Structurally-colored articles and methods for making and using structurally-colored articles

ABSTRACT

One or more aspects of the present disclosure are directed to bladders that incorporate a multi-layer optical film that impart a structural color to the bladder. The present disclosure is also directed to articles including the bladders having a multi-layer optical film, and methods for making articles and bladders having a multi-layer optical film.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of copending U.S. application Ser.No. 16/146,614, having the title “STRUCTURALLY COLORED ARTICLES ANDMETHODS OF MAKING STRUCTURALLY COLORED ARTICLES”, filed on Sep. 28,2018, which application claims the benefit of and priority to U.S.Provisional Application Ser. No. 62/565,299, having the title“STRUCTURALLY COLORED ARTICLES AND METHODS OF MAKING STRUCTURALLYCOLORED ARTICLES”, filed on Sep. 29, 2017, and to U.S. ProvisionalApplication Ser. No. 62/633,666, having the title “ARTICLES HAVINGSTRUCTURAL COLOR AND METHODS AND SYSTEMS FOR MAKING ARTICLES HAVINGSTRUCTURAL COLOR”, filed on Feb. 22, 2018, and to U.S. ProvisionalApplication Ser. No. 62/565,306, having the title “STRUCTURALLY COLOREDSTRUCTURES AND ARTICLES, METHODS OF MAKING STRUCTURES AND ARTICLES”,filed on Sep. 29, 2017, and to U.S. Provisional Application Ser. No.62/565,313, having the title “STRUCTURES HAVING STRUCTURAL COLOR ANDMETHODS AND SYSTEMS FOR MAKING STRUCTURES HAVING STRUCTURAL COLOR”,filed on Sep. 29, 2017, and U.S. Provisional Application Ser. No.62/565,310, having the title “STRUCTURES HAVING STRUCTURAL COLOR ANDMETHODS AND SYSTEMS FOR MAKING STRUCTURES HAVING STRUCTURAL COLOR”,filed on Sep. 29, 2017, the disclosures which are incorporated herein byreference in their entireties.

BACKGROUND

Structural color is caused by the physical interaction of light with themicro- or nano-features of a surface and the bulk material as comparedto color derived from the presence of dyes or pigments that absorb orreflect specific wavelengths of light based on the chemical propertiesof the dyes or pigments. Color from dyes and pigments can be problematicin a number of ways. For example, dyes and pigments and their associatedchemistries for fabrication and incorporation into finished goods maynot be environmentally friendly.

BRIEF DESCRIPTION OF THE DRAWINGS

Further aspects of the present disclosure will be more readilyappreciated upon review of the detailed description of its variousembodiments, described below, when taken in conjunction with theaccompanying drawings.

FIG. 1 illustrates an article of footwear that includes the multi-layeroptical films of the present disclosure.

FIG. 2 illustrates a side view of a portion of a bladder having anexemplary multi-layer optical film of the present disclosure.

FIGS. 3A-3B illustrate side views of exemplary multi-layer optical filmsof the present disclosure.

DESCRIPTION

The present disclosure provides for a bladder that is structurallycolored. The bladder includes a multi-layer optical film disposed on asurface of the bladder. The multi-layer optical film as disposed on thebladder has the characteristic of imparting a structural color (e.g., asingle-hue structural color, a multi-hue structural color, an iridescentstructural color, etc.). The structural color imparts an aestheticallyappealing color to the bladder without requiring the use of dyes orpigments and the environmental issues associated with their use. In oneembodiment, the bladder can be used in articles of footwear, componentsof footwear, articles of apparel, components of apparel, articles ofsports equipment, components of sports equipment, and the like.Additionally, the bladder can be used in other types of consumer goods.

The multi-layer optical film alone or optionally in combination with atextured surface (e.g., a textured layer or textured surface), oroptionally in combination with a primer layer, or optionally incombination with both a textured surface and a primer layer, can impartthe structural color. The optional textured surface and/or the primerlayer can be part of the multi-layer optical film or can be separatefrom the multi-layer optical film, but, when used with the multi-layeroptical film, combine to impart the structural color. In other words,while the multi-layer optical film alone can impart a first structuralcolor, the combination of the multi-layer optical film with the optionaltextured structure or primer layer or both can impart a secondstructural color, which differs from the first structural colormulti-layer optical film based on a color parameter such as hue,lightness, iridescence type. In such cases, the combination of themulti-layer optical film and the textured surface and/or the primerlayer can impart the structural color to the bladder.

After disposing the multi-layer optical film onto a side or surface of abladder wall or another component of the bladder, the bladder (e.g.,bladder wall) appears to be colored (i.e., to have a new, differentcolor than the surface of the bladder wall or component had prior to thedisposition) without the application of pigments or dyes to the bladder,although dyes and/or pigments can be used in conjunction with thestructural color. The multi-layer optical film can be disposed (e.g.,affixed, attached, adhered, bonded, joined) to an exterior-facing sideof the bladder, or an interior-facing side of the bladder. The bladdercan then be incorporated into an article, such as a sole or an upper foran article of footwear, for example. The article (e.g., the sole and/orupper) can be designed so that one or more portions of the bladderincluding the structurally colored bladder wall or component is visiblein the finished article, by including an opening, or a transparentcomponent covering the structurally colored component, and the like.

The present disclosure provides for an article comprising: a bladderhaving a first bladder wall having a first bladder wall thickness and anexterior-facing side comprising a first thermoplastic material and aninterior-facing side comprising a second thermoplastic material, whereinthe first bladder wall has a gas transmission rate of 15 cm³/m²·atm·dayor less for nitrogen for an average wall thickness of 20 mils; and amulti-layer optical film has a first side and a second side, wherein thefirst side and the second side are on opposing sides, wherein the firstside of the multi-layer optical film, the second side of the multi-layeroptical film, or both result in a structural color, wherein themulti-layer optical film is disposed on the exterior-facing side surfaceor the interior-facing side surface of the bladder or wherein themulti-layer optical film is disposed in an internal cavity of thebladder. The multi-layer optical film can include an optical layer. Atextured surface and/or a primer layer in combination with the opticallayer can result in the structural color. The present disclosure alsoprovides for an article of footwear or an article of sporting equipment,comprising cushioning element, wherein the cushioning element includes abladder. The present disclosure also provides for methods of making suchan article.

The present disclosure also provides for an inflated bladder comprisinga bladder wall having an interior-facing side and an exterior-facingside, wherein the interior-facing side defines at least a portion of aninterior region of the inflated bladder, and wherein the bladder wallfurther includes an average wall thickness between the interior-facingside and exterior-facing side that is less than 5 millimeters; and amulti-layer optical film having a first side and a second opposing side,wherein the first side of the multi-layer optical film is operablydisposed on the exterior-facing side of the bladder wall, and whereinthe multi-layer optical film imparts a structural color to the bladderwall. The present disclosure also provides for methods of making such anarticle. The present disclosure also provides for a bladder comprising abladder wall having an interior-facing side and an exterior-facing side,wherein the interior-facing side defines at least a portion of aninterior region of the bladder; a plurality of topographical structuresextending from the exterior-facing side of the bladder wall; and amulti-layer optical film having a first side and a second opposing side,wherein the first side of the multi-layer optical film is disposed onthe exterior-facing side of the bladder wall and covering the pluralityof topographical structures, and wherein the multi-layer optical filmimparts a structural color to the bladder wall. The present disclosurealso provides for methods of making such an article.

The present disclosure also provides for an article of footwearcomprising a footwear upper; and an inflated bladder comprising a topwall operably secured to the footwear upper; a bottom wall opposite thetop wall; and one or more sidewalls extending between the top wall andthe bottom wall of the inflated bladder, wherein the top wall, thebottom wall, and the one or more sidewalls collectively define aninterior region of the inflated bladder, and wherein the one or moresidewalls each comprise an exterior-facing side; and a multi-layeroptical film operably disposed on the exterior-facing side at least oneof the one or more sidewalls to impart a structural color to the one ormore sidewalls. The present disclosure also provides for methods ofmaking such an article.

In particular examples, a primer layer or a textured surface or both isincluded in the multi-layer optical film, or on the bladder. While manypossible materials can be used to form the primer layer, it has beenfound that using titanium dioxide in the primer material of the primerlayer, or using a primer material consisting essentially of titaniumdioxide, results in a primer layer which adheres well to flexiblepolymeric materials including polyurethanes.

While in many examples of this disclosure, an iridescent structuralcolor (i.e., a color which shifts over a wide range of hues when viewedfrom different angles) can be obtained, in other examples a structuralcolor which does not shift over a wide range of hues when viewed fromdifferent angles (e.g., a structural color which does not shift hues, orwhich shifts over a limited number of hues) also can be obtained.

In one example, the present disclosure provides for the multi-layeroptical film, as disposed onto the bladder, when measured according tothe CIE 1976 color space under a given illumination condition at threeobservation angles between −15 degrees and +60 degrees, has a firstcolor measurement at a first angle of observation having coordinates L₁*and a₁* and b₁*, and a second color measurement at a second angle ofobservation having coordinates L₂* and a₂* and b₂*, and a third colormeasurement at a third angle of observation having coordinates L₃* anda₃* and b₃*, wherein the L₁*, L₂*, and L₃* values may be the same ordifferent, wherein the a₁*, a₂*, and a₃* coordinate values may be thesame or different, wherein the b₁*, b₂*, and b₃* coordinate values maybe the same or different, and wherein the range of the combined a₁*, a₂*and a₃* values is less than about 40% of the overall scale of possiblea* values.

In another example, the present disclosure provides for the multi-layeroptical film, as disposed onto the bladder, when measured according tothe CIE 1976 color space under a given illumination condition at twoobservation angles between −15 degrees and +60 degrees, has a firstcolor measurement at a first angle of observation having coordinates L₁*and a₁* and b_(1*), and a second color measurement at a second angle ofobservation having coordinates L₂* and a₂* and b₂*, wherein the L₁* andL₂* values may be the same or different, wherein the a₁* and a₂*coordinate values may be the same or different, wherein the b₁* and b₂*coordinate values may be the same or different, and wherein the ΔE*_(ab)between the first color measurement and the second color measurement isless than or equal to about 100, whereΔE*_(ab)=[(L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂)²]^(1/2).

In yet another example, the present disclosure provides for themulti-layer optical film, as disposed onto the bladder, when measuredaccording to the CIELCH color space under a given illumination conditionat three observation angles between −15 degrees and +60 degrees, has afirst color measurement at a first angle of observation havingcoordinates L₁* and C₁* and h₁°, and a second color measurement at asecond angle of observation having coordinates L₂* and C₂* and h₁°, anda third color measurement at a third angle of observation havingcoordinates L₃* and C₃* and h₃°, wherein the L_(1*), L₂*, and L₃* valuesmay be the same or different, wherein the C_(1*), C₂*, and C₃*coordinate values may be the same or different, wherein the h₁°, h₂° andh₃° coordinate values may be the same or different, and wherein therange of the combined h₁°, h₂° and h₃° values is less than about 60degrees.

In an embodiment, the present disclosure provides for a method of makingan article of footwear comprising: providing a bladder as describedabove and herein; and incorporating the bladder onto a sole structure.In addition, the method includes affixing the sole structure to an upperstructure to form the article of footwear.

The present disclosure provides for a method of making a bladder,comprising: disposing a multi-layer optical film on a surface of abladder. The bladder can be a bladder having a first bladder wall havinga first bladder wall thickness and an exterior-facing side comprising afirst thermoplastic material and an interior-facing side comprising asecond thermoplastic material. Optionally, the first bladder wall has agas transmission rate of 15 cm³/m²·atm·day or less for nitrogen for anaverage wall thickness of 20 mils; and disposing a multi-layer opticalfilm onto at least one region of the bladder. The multi-layer opticalfilm has a first side and a second side, wherein the first side and thesecond side are on opposing sides, wherein the first side of themulti-layer optical film, the second side of the multi-layer opticalfilm, or both impart a structural color. The multi-layer optical filmcan be disposed on the exterior-facing side surface or theinterior-facing side surface of the bladder, or can be disposed in aninternal cavity of the bladder. The present disclosure also provides fora bladder formed using the method described above and herein.

Now having described embodiments of the present disclosure generally,additional discussion regarding embodiments will be described in greaterdetails.

This disclosure is not limited to particular embodiments described, andas such may, of course, vary. The terminology used herein serves thepurpose of describing particular embodiments only, and is not intendedto be limiting, since the scope of the present disclosure will belimited only by the appended claims.

Where a range of values is provided, each intervening value, to thetenth of the unit of the lower limit unless the context clearly dictatesotherwise, between the upper and lower limit of that range and any otherstated or intervening value in that stated range, is encompassed withinthe disclosure. The upper and lower limits of these smaller ranges mayindependently be included in the smaller ranges and are also encompassedwithin the disclosure, subject to any specifically excluded limit in thestated range. Where the stated range includes one or both of the limits,ranges excluding either or both of those included limits are alsoincluded in the disclosure.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features which may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentdisclosure. Any recited method may be carried out in the order of eventsrecited or in any other order that is logically possible.

Embodiments of the present disclosure will employ, unless otherwiseindicated, techniques of material science, chemistry, textiles, polymerchemistry, and the like, which are within the skill of the art. Suchtechniques are explained fully in the literature.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art of material science, chemistry, textiles, polymer chemistry, andthe like. Although methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of the presentdisclosure, suitable methods and materials are described herein.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” may include plural referents unless the contextclearly dictates otherwise. Thus, for example, reference to “a support”includes a plurality of supports. In this specification and in theclaims that follow, reference will be made to a number of terms thatshall be defined to have the following meanings unless a contraryintention is apparent.

The present disclosure provides for bladder that have structural color.The structural color can be produced using a multi-layer optical filmincorporated with the bladder. The multi-layer optical film can beincorporated into bladder, for example, on an exterior-facing side orsurface or an interior-facing side or surface of the bladder. Thebladder can be incorporated into a sole structure that can be affixed tothe upper optionally with other components to form the article offootwear. The sole structure and/or upper can be designed so that one ormore portions including the structural color are not covered up, includean opening, or otherwise exposed so that the structural color is visiblein the finished article of footwear and provides an aestheticallypleasing appearance.

In an aspect, the bladder can be incorporated into a number of differenttypes of articles of manufacture such as articles of footwear,components of footwear, articles of apparel, components of apparel,articles of sporting equipment, and components of sporting equipment.For example, the bladder can be used as a cushioning element onceinflated (e.g., fluid-filled bladder). In particular, the articles ofmanufacture can include footwear (e.g., dress shoes, athletic footwear,hiking boots, work boots, or the like), skates (e.g., hockey skates,figure skates, in-line skates, roller skates, or the like), apparel(e.g., shirts, jerseys, pants, shorts, gloves, glasses, socks, hats,caps, jackets, undergarments) or components thereof, containers (e.g.,backpacks, bags), and upholstery for furniture (e.g., chairs, couches,car seats), bed coverings (e.g., sheets, blankets), table coverings,towels, flags, tents, sails, and parachutes. In addition, the bladdercan be used to produce articles or other items that are disposed on thearticle, where the article can be striking devices (e.g., bats, rackets,sticks, mallets, golf clubs, paddles, etc.), athletic equipment (e.g.,golf bags, baseball and football gloves, soccer ball restrictionstructures), protective equipment (e.g., pads, helmets, guards, visors,masks, goggles, etc.), locomotive equipment (e.g., bicycles,motorcycles, skateboards, cars, trucks, boats, surfboards, skis,snowboards, etc.), balls or pucks for use in various sports, fishing orhunting equipment, furniture, electronic equipment, constructionmaterials, eyewear, timepieces, jewelry, and the like. In an aspect, thebladder can be used as a cushioning element in the strap of a backpackor other bag.

The footwear can be designed for a variety of uses, such as sporting,athletic, military, work-related, recreational, or casual use.Primarily, the article of footwear is intended for outdoor use onunpaved surfaces (in part or in whole), such as on a ground surfaceincluding one or more of grass, turf, gravel, sand, dirt, clay, mud, andthe like, whether as an athletic performance surface or as a generaloutdoor surface. However, the article of footwear may also be desirablefor indoor applications, such as indoor sports including dirt playingsurfaces for example (e.g., indoor baseball fields with dirt infields).

The article of footwear is designed for use in outdoor sportingactivities, such as global football/soccer, golf, American football,rugby, baseball, running, track and field, cycling (e.g., road cyclingand mountain biking), and the like. The article of footwear canoptionally include traction elements (e.g., lugs, cleats, studs, andspikes as well as tread patterns) to provide traction on soft andslippery surfaces, where components of the present disclosure can beused or applied between or among the traction elements and optionally onthe sides of the traction elements but on the surface of the tractionelement that contacts the ground or surface. Cleats, studs and spikesare commonly included in footwear designed for use in sports such asglobal football/soccer, golf, American football, rugby, baseball, andthe like, which are frequently played on unpaved surfaces. Lugs and/orexaggerated tread patterns are commonly included in footwear includingboots design for use under rugged outdoor conditions, such as trailrunning, hiking, and military use.

When the bladder is incorporated into footwear, the bladder can beincorporated into a sole structure that can be affixed to an upper aswell as other components to form the footwear. In an aspect, the soleand/or upper can be designed so that one or more portions of the bladderare not covered up, include an opening, or otherwise exposed so that thestructural color can be observed.

FIG. 1 illustrates an article of footwear having a bladder 11 thatincludes the multi-layer optical film of the present disclosure. Themulti-layer optical film is represented by hashed area 12. The locationof the multi-layer optical film is provided only to indicate onepossible area that the multi-layer optical film can be located. Also,one location is illustrated in the figure, but this is done only forillustration purposes as the bladder can include one or a plurality ofmulti-layer optical films, where the size and location can be determinedbased on the item. The multi-layer optical film(s) located can representa number, letter, symbol, design, emblem, graphic mark, icon, logo, orthe like.

FIG. 2 illustrates a cross-section of the bladder that illustrate onepossible location of the multi-layer optical film on a first bladderwall. As shown in FIG. 2, the first bladder wall 190 has a core layer206 having a plurality of layers, optionally a cap layer 214, optionallya primer layer 204, optionally a textured structure or a textured layer202, and a multi-layer optical film 200. Optionally, the position of theprimer layer 204 and the textured structure or textured layer 202 can bereversed (not shown). Optionally, the cap layer 214 can be formed of thefirst thermoplastic material, and can include a textured surface (notshown). Alternatively or additionally, the side of the multi-layeroptical film 200 facing the cap layer 214 can include a primer layer, ora textured surface, or both.

Bladders of the present disclosure include the multi-layer optical filmthat has the characteristic of producing optical effects such asstructural color. The multi-layer optical film includes at least oneoptical layer (e.g., a multilayer reflector or a multilayer filter)optionally in combination with a textured surface (e.g., integral to themulti-layer optical film or as part of the surface of the bladder),optionally with a primer layer, optionally with a protective layer, oroptionally with any combination of the textured surface, the primerlayer, and the protective layer. The multi-layer optical film or thecombination of the multi-layer optical film optionally with the texturedsurface and/or primer layer impart structural color (e.g., single color,multicolor, iridescent), to the bladder. Following disposing of themulti-layer optical film on the bladder, the bladder appears to becolored, for example a new, different, or more intense color (e.g., inhue or otherwise defined herein) than the surface of the article hadprior to the disposing, and this can be achieved with or without theapplication of pigments or dyes to the bladder to produce aestheticallypleasing effects.

As has been described herein, the structural color can include one of anumber of colors. The “color” of an bladder as perceived by a viewer candiffer from the actual color of the bladder, as the color perceived by aviewer is determined by the actual color of the bladder, by the viewer'sability to detect the wavelengths of light reflected by the bladder, bythe wavelengths of light used to illuminate the bladder, as well asother factors such as the coloration of the environment of the bladder,and the type of incident light (e.g., sunlight, fluorescent light, andthe like). As a result, the color of an object as perceived by a viewercan differ from the actual color of the bladder.

Conventionally, color is imparted to man-made objects by applyingcolored pigments or dyes to the object. More recently, methods ofimparting “structural color” to man-made objects have been developed.Structural color is color which is produced, at least in part, bymicroscopically structured surfaces that interfere with visible lightcontacting the surface. The structural color is color caused by physicalphenomena including the scattering, refraction, reflection,interference, and/or diffraction of light, unlike color caused by theabsorption or emission of visible light through coloring matters. Forexample, optical phenomena which result in structural color can includemultilayer interference, thin-film interference, refraction, dispersion,light scattering, Mie scattering, diffraction, and diffraction grating.In various aspects described herein, structural color imparted to anarticle can be visible to a viewer having 20/20 visual acuity and normalcolor vision from a distance of about 1 meter from the article.

The structural color can be angle-independent structural color in thatthe hue, the hue and value, or the hue, value and chroma observed isindependent of or substantially (e.g., about 90 percent, about 95percent, or about 99 percent) independent of the angle of observation.For example, the angle-independent structural color can display the samehue or substantially the same hue when viewed from at least 3 differentangles that are at least 15 degrees apart from each other (e.g.,single-hue structural color).

As described herein, structural color is produced, at least in part, bythe multi-layer optical film, as opposed to the color being producedsolely by pigments and/or dyes. The coloration of a structurally-coloredbladder can be due solely to structural color (i.e., the bladder, acolored portion of the bladder, or a colored outer layer of the bladdercan be substantially free of pigments and/or dyes). Structural color canalso be used in combination with pigments and/or dyes, for example, toalter all or a portion of a structural color.

“Hue” is commonly used to describe the property of color which isdiscernible based on a dominant wavelength of visible light, and isoften described using terms such as magenta, red, orange, yellow, green,cyan, blue, indigo, violet, etc. or can be described in relation (e.g.,as similar or dissimilar) to one of these. The hue of a color isgenerally considered to be independent of the intensity or lightness ofthe color. For example, in the Munsell color system, the properties ofcolor include hue, value (lightness) and chroma (color purity).Particular hues are commonly associated with particular ranges ofwavelengths in the visible spectrum: wavelengths in the range of about700 to 635 nanometers are associated with red, the range of about 635 to590 nanometers is associated with orange, the range of about 590 to 560nanometers is associated with yellow, the range of about 560 to 520nanometers is associated with green, the range of about 520 to 490nanometers is associated with cyan, the range of about 490 nanometers to450 nanometers is associated with blue, and the range of about 450 to400 nanometers is associated with violet.

The color (including the hue) of a bladder as perceived by a viewer candiffer from the actual color of the bladder. The color as perceived by aviewer depends not only on the physics of the bladder, but also itsenvironment, and the characteristics of the perceiving eye and brain.For example, as the color perceived by a viewer is determined by theactual color of the bladder (e.g., the color of the light leaving thesurface of the bladder), by the viewer's ability to detect thewavelengths of light reflected or emitted by the bladder, by thewavelengths of light used to illuminate the bladder, as well as otherfactors such as the coloration of the environment of the bladder, andthe type of incident light (e.g., sunlight, fluorescent light, and thelike). As a result, the color of an object as perceived by a viewer candiffer from the actual color of the bladder.

When used in the context of structural color, one can characterize thehue of a structurally-colored article (bladder), i.e., an article (e.g.,bladder) that has been structurally colored by incorporating an opticalelement into the article, based on the wavelengths of light thestructurally-colored portion of the article absorbs and reflects (e.g.,linearly and non-linearly). While the optical element may impart a firststructural color, the presence of an optional textured surface and/orprimer layer can alter the structural color. Other factors such ascoatings or transparent elements may further alter the perceivedstructural color. The hue of the structurally colored article caninclude any of the hues described herein as well as any other hues orcombination of hues. The structural color can be referred to as a“single hue” (i.e., the hue remains substantially the same, regardlessof the angle of observation and/or illumination), or “multihued” (i.e.,the hue varies depending upon the angle of observation and/orillumination). The multihued structural color can be iridescent (i.e.,the hue changes gradually over two or more hues as the angle ofobservation or illumination changes). The hue of an iridescent multihuedstructural color can change gradually across all the hues in the visiblespectrum (e.g., like a “rainbow”) as the angle of observation orillumination changes. The hue of an iridescent multihued structuralcolor can change gradually across a limited number of hues in thevisible spectrum as the angle of observation or illumination changes, inother words, one or more hues in the visible spectrum (e.g., red,orange, yellow, etc.) are not observed in the structural color as theangle of observation or illumination changes. Only one hue, orsubstantially one hue, in the visible spectrum may be present for asingle-hued structural color. The hue of a multihued structural colorcan change more abruptly between a limited number of hues (e.g., between2-8 hues, or between 2-4 hues, or between 2 hues) as the angle ofobservation or illumination changes.

The structural color can be a multi-hued structural color in which twoor more hues are imparted by the structural color.

The structural color can be iridescent multi-hued structural color inwhich the hue of the structural color varies over a wide number of hues(e.g., 4, 5, 6, 7, 8 or more hues) when viewed at a single viewingangle, or when viewed from two or more different viewing angles that areat least 15 degrees apart from each other.

The structural color can be limited iridescent multi-hue structuralcolor in which the hue of the structural color varies, or variessubstantially (e.g., about 90 percent, about 95 percent, or about 99percent) over a limited number of hues (e.g., 2 hues, or 3 hues) whenviewed from two or more different viewing angles that are at least 15degrees apart from each other. In some aspects, a structural colorhaving limited iridescence is limited to two, three or four huesselected from the RYB primary colors of red, yellow and blue, optionallythe RYB primary and secondary colors of red, yellow, blue, green, orangeand purple, or optionally the RYB primary, secondary and tertiary colorsof red, yellow, blue, green, orange purple, green-yellow, yellow-orange,orange-red, red-purple, purple-blue, and blue-green.

The structural color can be single-hue angle-independent structuralcolor in which the hue, the hue and value, or the hue, value and chromaof the structural color is independent of or substantially (e.g., about90 percent, about 95 percent, or about 99 percent) independent of theangle of observation. For example, the single-hue angle-independentstructural color can display the same hue or substantially the same huewhen viewed from at least 3 different angles that are at least 15degrees apart from each other (e.g., single-hue structural color).

The structural color imparted can be a structural color having limitediridescence such that, when each color observed at each possible angleof observation is assigned to a single hue selected from the groupconsisting of the primary, secondary and tertiary colors on the redyellow blue (RYB) color wheel, for a single structural color, all of theassigned hues fall into a single hue group, wherein the single hue groupis one of a) green-yellow, yellow, and yellow-orange; b) yellow,yellow-orange and orange; c) yellow-orange, orange, and orange-red; d)orange-red, and red-purple; e) red, red-purple, and purple; f)red-purple, purple, and purple-blue; g) purple, purple-blue, and blue;h) purple-blue, blue, and blue-green; i) blue, blue-green and green; andj) blue-green, green, and green-yellow. In other words, in this exampleof limited iridescence, the hue (or the hue and the value, or the hue,value and chroma) imparted by the structural color varies depending uponthe angle at which the structural color is observed, but the hues ofeach of the different colors viewed at the various angles ofobservations varies over a limited number of possible hues. The huevisible at each angle of observation can be assigned to a singleprimary, secondary or tertiary hue on the red yellow blue (RYB) colorwheel (i.e., the group of hues consisting of red, yellow, blue, green,orange purple, green-yellow, yellow-orange, orange-red, red-purple,purple-blue, and blue-green). For example, while a plurality ofdifferent colors are observed as the angle of observation is shifted,when each observed hue is classified as one of red, yellow, blue, green,orange purple, green-yellow, yellow-orange, orange-red, red-purple,purple-blue, and blue-green, the list of assigned hues includes no morethan one, two, or three hues selected from the list of RYB primary,secondary and tertiary hues. In some examples of limited iridescence,all of the assigned hues fall into a single hue group selected from huegroups a)-j), each of which include three adjacent hues on the RYBprimary, secondary and tertiary color wheel. For example, all of theassigned hues can be a single hue within hue group h) (e.g., blue), orsome of the assigned hues can represent two hues in hue group h) (e.g.,purple-blue and blue), or can represent three hues in hue group h)(e.g., purple-blue, blue, and blue-green).

Similarly, other properties of the structural color, such as thelightness of the color, the saturation of the color, and the purity ofthe color, among others, can be substantially the same regardless of theangle of observation or illumination, or can vary depending upon theangle of observation or illumination. The structural color can have amatte appearance, a glossy appearance, or a metallic appearance, or acombination thereof.

As discussed above, the color (including hue) of a structurally-coloredbladder can vary depending upon the angle at which thestructurally-colored bladder is observed or illuminated. The hue or huesof a bladder can be determined by observing the bladder, or illuminatingthe bladder, at a variety of angles using constant lighting conditions.As used herein, the “angle” of illumination or viewing is the anglemeasured from an axis or plane that is orthogonal to the surface. Theviewing or illuminating angles can be set between about 0 and 180degrees. The viewing or illuminating angles can be set at 0 degrees, 15degrees, 30 degrees, 45 degrees, 60 degrees, and −15 degrees and thecolor can be measured using a colorimeter or spectrophotometer (e.g.,Konica Minolta), which focuses on a particular area of the bladder tomeasure the color. The viewing or illuminating angles can be set at 0degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, 75 degrees, 90degrees, 105 degrees, 120 degrees, 135 degrees, 150 degrees, 165degrees, 180 degrees, 195 degrees, 210 degrees, 225 degrees, 240degrees, 255 degrees, 270 degrees, 285 degrees, 300 degrees, 315degrees, 330 degrees, and 345 degrees and the color can be measuredusing a colorimeter or spectrophotometer. In a particular example of amultihued bladder colored using only structural color, when measured at0 degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, and −15degrees, the hues measured for bladder consisted of “blue” at three ofthe measurement angles, “blue-green” at 2 of the measurement angles and“purple” at one of the measurement angles.

In other embodiments, the color (including hue, value and/or chroma) ofa structurally-colored bladder does not change substantially, if at all,depending upon the angle at which the bladder is observed orilluminated. In instances such as this the structural color can be anangle-independent structural color in that the hue, the hue and value,or the hue, value and chroma observed is substantially independent or isindependent of the angle of observation.

Various methodologies for defining color coordinate systems exist. Oneexample is L*a*b* color space, where, for a given illuminationcondition, L* is a value for lightness, and a* and b* are values forcolor-opponent dimensions based on the CIE coordinates (CIE 1976 colorspace or CIELAB). In an embodiment, a structurally-colored bladderhaving structural color can be considered as having a “single” colorwhen the change in color measured for the bladder is within about 10% orwithin about 5% of the total scale of the a* or b* coordinate of theL*a*b* scale (CIE 1976 color space) at three or more measuredobservation or illumination angles selected from measured at observationor illumination angles of 0 degrees, 15 degrees, 30 degrees, 45 degrees,60 degrees, and −15 degrees. In certain embodiments, colors which, whenmeasured and assigned values in the L*a*b* system that differ by atleast 5 percent of the scale of the a* and b* coordinates, or by atleast 10 percent of the scale of the a* and b* coordinates, areconsidered to be different colors. The structurally-colored bladder canhave a change of less than about 40%, or less than about 30%, or lessthan about 20%, or less than about 10%, of the total scale of the a*coordinate or b* coordinate of the L*a*b* scale (CIE 1976 color space)at three or more measured observation or illumination angles.

A change in color between two measurements in the CIELAB space can bedetermined mathematically. For example, a first measurement hascoordinates L_(1*), a₁* and b_(1*), and a second measurement hascoordinates L_(2*), a₂* and b₂*. The total difference between these twomeasurements on the CIELAB scale can be expressed as E*ab, which iscalculated as follows:ΔE*_(ab)=[(L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²]^(1/2). Generally speaking,if two colors have a E*ab of less than or equal to 1, the difference incolor is not perceptible to human eyes, and if two colors have a E*ab ofgreater than 100 the colors are considered to be opposite colors, whilea E*ab of about 2-3 is considered the threshold for perceivable colordifference. In certain embodiments, a structurally colored bladderhaving structural color can be considered as having a “single” colorwhen the ΔE*_(ab) is less than 60, or less than 50, or less than 40, orless than 30, between three or more measured observation or illuminationangles selected from measured at observation or illumination angles of 0degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, and −15degrees. The structurally-colored bladder can have a ΔE*ab that is lessthan about 100, or less than about 80, or less than about 60, betweentwo or more measured observation or illumination angles.

Another example of a color scale is the CIELCH color space, where, for agiven illumination condition, L* is a value for lightness, C* is a valuefor chrome, and h° denotes a hue as an angular measurement. In anembodiment, a structurally-colored bladder having structural color canbe considered as having a “single” color when the color measured for thebladder is less than 10 degrees different or less than 5 degreesdifferent at the h° angular coordinate of the CIELCH color space, atthree or more measured observation or illumination angles selected frommeasured at observation or illumination angles of 0 degrees, 15 degrees,30 degrees, 45 degrees, 60 degrees, and −15 degrees. In certainembodiments, colors which, when measured and assigned values in theCIELCH system that vary by at least 45 degrees in the h° measurements,are considered to be different colors The structurally-colored bladdercan have a change of less than about 60 degrees, or less than about 50degrees, or less than about 40 degrees, or less than about 30 degrees,or less than about 20 degrees, or less than about 10 degrees, in the h°measurements of the CIELCH system at three or more measured observationor illumination angles.

Another system for characterizing color includes the “PANTONE” MatchingSystem (Pantone LLC, Carlstadt, N.J., USA), which provides a visualcolor standard system to provide an accurate method for selecting,specifying, broadcasting, and matching colors through any medium. In anexample, a structurally-colored bladder having a structural color can beconsidered as having a “single” color when the color measured for thebladder is within a certain number of adjacent standards, e.g., within20 adjacent PANTONE standards, at three or more measured observation orillumination angles selected from 0 degrees, 15 degrees, 30 degrees, 45degrees, 60 degrees, and −15 degrees.

Now having described color, additional details regarding the multi-layeroptical film are provided. As described herein, the article includes themulti-layer optical film. The multi-layer optical film includes at leastone optical layer. The multi-layer optical film that can be or include asingle or multilayer reflector or a multilayer filter. The multi-layeroptical film can function to modify the light that impinges thereupon sothat structural color is imparted to the article. The multi-layeroptical film can include at least one optical layer and optionally oneor more additional layers (e.g., a protective layer, the textured layer,the primer layer, a polymer layer, and the like).

The method of making the structurally colored article can includedisposing (e.g., affixing, attaching, bonding, fastening, joining,appending, connecting, binding and includes operably disposing etc.) themulti-layer optical film onto an article (e.g., an article of footwear,an article of apparel, an article of sporting equipment, etc.). Thearticle includes a component, and the component has a surface upon whichthe multi-layer optical film can be disposed. The surface of the articlecan be made of a material such as a thermoplastic material or thermosetmaterial, as described herein. For example, the article has a surfaceincluding a thermoplastic material (i.e., a first thermoplasticmaterial), for example an externally-facing surface of the component oran internally-facing surface of the component (e.g., anexternally-facing surface or an internally-facing surface a bladder).The multi-layer optical film can be disposed onto the thermoplasticmaterial, for example.

The multi-layer optical film has a first side (including the outersurface) and a second side opposing the first side (including theopposing outer surface), where the first side or the second side isadjacent the article. For example, when the multi-layer optical film isused in conjunction with a component having internally-facing andexternally-facing surfaces, such as a film or a bladder, the first sideof the multi-layer optical film can be disposed on the internally-facingsurface of the component, such as in the following order: second side ofthe multi-layer optical film/core of the multi-layer optical film/firstside of the multi-layer optical film/internally-facing surface of thecomponent/core of the component/externally-facing surface of thecomponent. Alternatively, the second side the multi-layer optical filmcan be disposed on the internally-facing surface of the component, suchas in the following order: first side of the multi-layer opticalfilm/core of the multi-layer optical film/second side of the multi-layeroptical film/internally-facing surface of the component/core of thecomponent wall/externally-facing surface of the component. In anotherexample, the first side of the multi-layer optical film can be disposedon the externally-facing surface of the component, such as in thefollowing order: internally-facing surface of the component/core of thecomponent/externally-facing surface of the component/first side of themulti-layer optical film/core of the multi-layer optical film/secondside of the multi-layer optical film. Similarly, the second side of themulti-layer optical film can be disposed on the externally-facingsurface of the component, such as in the following order:internally-facing surface of the component/core of thecomponent/externally-facing surface of the component/second side of themulti-layer optical film/core of the multi-layer optical film/first sideof the multi-layer optical film. In examples where the optional texturedsurface, the optional primer layer, or both are present, the texturedsurface and/or the primer layer can be located at the interface betweenthe surface of the component and a side of the multi-layer optical film.

The multi-layer optical film or layers or portions thereof (e.g.,optical layer) can be formed using known techniques such as physicalvapor deposition, electron beam deposition, atomic layer deposition,molecular beam epitaxy, cathodic arc deposition, pulsed laserdeposition, sputtering deposition (e.g., radio frequency, directcurrent, reactive, non-reactive), chemical vapor deposition,plasma-enhanced chemical vapor deposition, low pressure chemical vapordeposition and wet chemistry techniques such as layer-by-layerdeposition, sol-gel deposition, Langmuir Blodgett, and the like. Thetemperature of the first side can be adjusted using the technique toform the multi-layer optical film and/or a separate system to adjust thetemperature. Additional details are provided herein.

The optical layer(s) of the multi-layer optical film can comprise amultilayer reflector. The multilayer reflector can be configured to havea certain reflectivity at a given wavelength of light (or range ofwavelengths) depending, at least in part, on the material selection,thickness and number of the layers of the multilayer reflector. In otherwords, one can carefully select the materials, thicknesses, and numbersof the layers of a multilayer reflector and optionally its interactionwith one or more other layers, so that it can reflect a certainwavelength of light (or range of wavelengths), to produce a desiredstructural color. The optical layer can include at least two adjacentlayers, where the adjacent layers have different refractive indices. Thedifference in the index of refraction of adjacent layers of the opticallayer can be about 0.0001 to 50 percent, about 0.1 to 40 percent, about0.1 to 30 percent, about 0.1 to 20 percent, about 0.1 to 10 percent (andother ranges there between (e.g., the ranges can be in increments of0.0001 to 5 percent)). The index of refraction depends at least in partupon the material of the optical layer and can range from 1.3 to 2.6.

The optical layer(s) can include 2 to 20 layers, 2 to 10 layer, 2 to 6layers, or 2 to 4 layers. Each layer of the optical layer can have athickness that is about one-fourth of the wavelength of light to bereflected to produce the desired structural color. Each layer of theoptical layer can have a thickness of about 10 to 500 nanomerters orabout 90 to 200 nanometers. The optical layer can have at least twolayers, where adjacent layers have different thicknesses and optionallythe same or different refractive indices.

The multi-layer optical film can comprise a multilayer filter. Themultilayer filter destructively interferes with light that impinges uponthe bladder, where the destructive interference of the light andoptionally interaction with one or more other layers or structures(e.g., a multilayer reflector, a textured structure) result in thestructural color. In this regard, the layers of the multilayer filtercan be designed (e.g., material selection, thickness, number of layer,and the like) so that a single wavelength of light, or a particularrange of wavelengths of light, make up the structural color. Forexample, the range of wavelengths of light can be limited to a rangewithin plus or minus 30 percent of a single wavelength, or within plusor minus 20 percent of a single wavelength, or within plus or minus 10percent of a single wavelength, or within plus or minus 5 percent or asingle wavelength. The range of wavelengths can be broader to produce amore iridescent structural color.

The optical layer(s) can include multiple layers where each layerindependently comprises a material selected from: the transition metals,the metalloids, the lanthanides, and the actinides, as well as nitrides,oxynitrides, sulfides, sulfates, selenides, and tellurides of these. Thematerial can be selected to provide an index of refraction that whenoptionally combined with the other layers of the multi-layer opticalfilm achieves the desired result. One or more layers of the opticallayer can be made of liquid crystals. Each layer of the optical layercan be made of liquid crystals. One or more layers of the optical layercan be made of a material such as: silicon dioxide, titanium dioxide,zinc sulfide, magnesium fluoride, tantalum pentoxide, aluminum oxide, ora combination thereof. Each layer of the optical layer can be made of amaterial such as: silicon dioxide, titanium dioxide, zinc sulfide,magnesium fluoride, tantalum pentoxide, aluminum oxide, or a combinationthereof.

The multi-layer optical film can be uncolored (e.g., no pigments or dyesadded to the structure or its layers), colored (e.g., pigments and/ordyes are added to the structure or its layers (e.g., dark or blackcolor)), reflective, and/or transparent (e.g., percent transmittance of75 percent or more). The side upon which the multi-layer optical film isdisposed can be uncolored (e.g., no pigments or dyes added to thematerial), colored (e.g., pigments and/or dyes are added to the material(e.g., dark or black color)), reflective, and/or transparent (e.g.,percent transmittance of 75 percent or more).

The optical layer(s) can be formed in a layer-by-layer manner, whereeach layer has a different index of refraction. Each layer of theoptical layer can be formed using known techniques such as physicalvapor deposition including: chemical vapor deposition, pulsed laserdeposition, evaporative deposition, sputtering deposition (e.g., radiofrequency, direct current, reactive, non-reactive), plasma enhancedchemical vapor deposition, electron beam deposition, atomic layerdeposition, molecular beam epitaxy, cathodic arc deposition, lowpressure chemical vapor deposition and wet chemistry techniques such aslayer by layer deposition, sol-gel deposition, Langmuir-Blodgett and thelike.

As mentioned above, the multi-layer optical film can include one or morelayers in addition to the optical layer(s). The multi-layer optical filmhas a first side (e.g., the side having a surface) and a second side(e.g., the side having a surface), where the first side or the secondside is adjacent the surface of the component. The one or more otherlayers of the multi-layer optical film can be on the first side and/orthe second side of the multi-layer optical film. For example, themulti-layer optical film can include a protective layer and/or apolymeric layer such as a thermoplastic polymeric layer, where theprotective layer and/or the polymeric layer can be on one or both of thefirst side and the second side of the multi-layer optical film. Inanother example, the multi-layer optical film can include a primer layeras described herein. One or more of the optional other layers caninclude a textured surface. Alternatively or in addition, one or moreoptical layers of the multi-layer optical film can include a texturedsurface.

A protective layer can be disposed on the first and/or second side ofthe optical layer to protect the optical layer. The protective layer ismore durable or more abrasion resistant than the optical layer. Theprotective layer is optically transparent to visible light. Theprotective layer can be on the first side of the multi-layer opticalfilm to protect the optical layer. All or a portion of the protectivelayer can include a dye or pigment in order to alter an appearance ofthe structural color. The protective layer can include silicon dioxide,glass, combinations of metal oxides, or mixtures of polymers. Theprotective layer can have a thickness of about 3 nanometers to 1millimeter.

The protective layer can be formed using physical vapor deposition,chemical vapor deposition, pulsed laser deposition, evaporativedeposition, sputtering deposition (e.g., radio frequency, directcurrent, reactive, non-reactive), plasma enhanced chemical vapordeposition, electron beam deposition, cathodic arc deposition, lowpressure chemical vapor deposition and wet chemistry techniques such aslayer by layer deposition, sol-gel deposition, Langmuir-Blodgett, andthe like. Alternatively or in addition, the protective layer can beapplied by spray coating, dip coating, brushing, spin coating, doctorblade coating, and the like.

A polymeric layer can be disposed on the first and/or the second side ofthe multi-layer optical film. The polymeric layer can be used to disposethe multi-layer optical film onto an article, such as, for example, whenthe article does not include a thermoplastic material to adhere themulti-layer optical film. The polymeric layer can comprise a polymericadhesive material, such as a hot melt adhesive. The polymeric layer canbe a thermoplastic material and can include one or more layers. Thethermoplastic material can be any one of the thermoplastic materialsdescribed herein. The polymeric layer can be applied using variousmethodologies, such as spin coating, dip coating, doctor blade coating,and so on. The polymeric layer can have a thickness of about 3nanometers to 1 millimeter.

As described above, one or more embodiments of the present disclosureprovide articles that incorporate the multi-layer optical film (e.g.,single or multilayer structures) on a side of a component of the articleto impart structural color. The multi-layer optical film can be disposedonto the thermoplastic material of the side of the article, and the sideof the article can include a textile, including a textile comprising thethermoplastic material.

Having described the structural color structure, additional details willnow be described for the optional textured surface. As described herein,the component includes the multi-layer optical film and the multi-layeroptical film can include at least one optical layer and optionally atextured surface. The textured surface can be a surface of a texturedstructure or a textured layer. The textured surface may be provided aspart of the multi-layer optical film. For example, the multi-layeroptical film may comprise a textured layer or a textured structure thatcomprises the textured surface. The textured surface may be formed onthe first or second side of the multi-layer optical film. For example, aside of the optical layer may be formed or modified to provide atextured surface, or a textured layer or textured structure can beaffixed to the first or second side of the multi-layer optical film. Thetextured surface may be provided as part of the component to which themulti-layer optical film is disposed. For example, the multi-layeroptical film may be disposed onto the surface of the component where thesurface of the component is a textured surface, or the surface of thecomponent includes a textured structure or a textured layer affixed toit.

The textured surface (or a textured structure or textured layerincluding the textured surface) may be provided as a feature on or partof another medium, such as a transfer medium, and imparted to a side orlayer of the multi-layer optical film or to the surface of thecomponent. For example, a mirror image or relief form of the texturedsurface may be provided on the side of a transfer medium, and thetransfer medium contacts a side of the multi-layer optical film or thesurface of the component in a way that imparts the textured surface tothe multi-layer optical film or article. While the various embodimentsherein may be described with respect to a textured surface of themulti-layer optical film, it will be understood that the features of thetextured surface, or a textured structure or textured layer, may beimparted in any of these ways.

The textured surface can contribute to the structural color resultingfrom the multi-layer optical film. As described herein, structuralcoloration is imparted, at least in part, due to optical effects causedby physical phenomena such as scattering, diffraction, reflection,interference or unequal refraction of light rays from a multi-layeroptical film. The textured surface (or its mirror image or relief) caninclude a plurality of profile features and flat or planar areas. Theplurality of profile features included in the textured surface,including their size, shape, orientation, spatial arrangement, etc., canaffect the light scattering, diffraction, reflection, interferenceand/or refraction resulting from the multi-layer optical film. The flator planar areas included in the textured surface, including their size,shape, orientation, spatial arrangement, etc., can affect the lightscattering, diffraction, reflection, interference and/or refractionresulting from the multi-layer optical film. The desired structuralcolor can be designed, at least in part, by adjusting one or more ofproperties of the profile features and/or flat or planar areas of thetextured surface.

The profile features (also referred to as “topographical structures”)can extend from a side of the flat areas, so as to provide theappearance of projections and/or depressions therein. A profile featuremay include various combinations of projections and depressions. Forexample, a profile feature may include a projection with one or moredepressions therein, a depression with one or more projections therein,a projection with one or more further projections thereon, a depressionwith one or more further depressions therein, and the like. The flatareas do not have to be completely flat and can include texture,roughness, and the like. The texture of the flat areas may notcontribute much, if any, to the imparted structural color. The textureof the flat areas typically contributes to the imparted structuralcolor. For clarity, the profile features and flat areas are described inreference to the profile features extending above the flat areas, butthe inverse (e.g., dimensions, shapes, and the like) can apply when theprofile features are depressions in the textured structure.

The textured surface can comprise a thermoplastic material or athermoset material. The profile features and the flat areas can beformed using a thermoplastic material. For example, when thethermoplastic material is heated above its softening temperature atextured surface can be formed in the thermoplastic material such as bymolding, stamping, printing, compressing, cutting, etching, vacuumforming, etc., the thermoplastic material to form profile features andflat areas therein. The textured surface can be imparted on a side of athermoplastic material. The textured surface can be formed in a layer ofthermoplastic material. The profile features and the flat areas can bemade of the same thermoplastic material or a different thermoplasticmaterial. In an embodiment, the exterior-facing side or surface and/orthe interior-facing side or surface of the bladder can be made of athermoplastic material and the textured surface or textured surface canbe formed as described.

The textured surface generally has a length dimension extending along anx-axis, and a width dimension extending along a z-axis, and a thicknessdimension extending along a y-axis. The textured surface has a generallyplanar portion extending in a first plane that extends along the x-axisand the z-axis. A profile feature can extend outward from the firstplane, so as to extend above or below the plane x. A profile feature mayextend generally orthogonal to the first plane, or at an angle greaterto or less than 90 degrees to the first plane.

The dimension (e.g., length, width, height, diameter, depending upon theshape of the profile feature) of each profile feature can be within thenanometer to micrometer range. A textured surface can have a profilefeature and/or flat area with a dimension of about 10 nanometers toabout 500 micrometers. The profile feature can have dimensions in thenanometer range, e.g., from about 10 nanometers to about 1000nanometers. All of the dimensions of the profile feature (e.g., length,width, height, diameter, depending on the geometry) can be in thenanometer range, e.g., from about 10 nanometers to about 1000nanometers. The textured surface can have a plurality of profilefeatures having dimensions that are 1 micrometer or less. In thiscontext, the phrase “plurality of the profile features” is meant to meanthat about 50 percent or more, about 60 percent or more, about 70percent or more, about 80 percent or more, about 90 percent or more, orabout 99 percent or more of the profile features have a dimension inthis range. The profile features can have a ratio of width:height and/orlength:height dimensions of about 1:2 and 1:100, or 1:5 and 1:50, or 1:5and 1:10.

The textured surface can have a profile feature and/or flat area with adimension within the micrometer range of dimensions. A textured surfacecan have a profile feature and/or flat area with a dimension of about 1micrometer to about 500 micrometers. All of the dimensions of theprofile feature (e.g., length, width, height, diameter, depending on thegeometry) can be in the micrometer range, e.g., from about 1 micrometerto about 500 micrometers. The textured surface can have a plurality ofprofile features having dimensions that are from about 1 micrometer toabout 500 micrometer. In this context, the phrase “plurality of theprofile features” is meant to mean that about 50 percent or more, about60 percent or more, about 70 percent or more, about 80 percent or more,about 90 percent or more, or about 99 percent or more of the profilefeatures have a dimension in this range. The height of the profilefeatures (or depth if depressions) can be about 0.1 and 50 micrometers,about 1 to 5 micrometers, or 2 to 3 micrometers. The profile featurescan have a ratio of width:height and/or length:height dimensions ofabout 1:2 and 1:100, or 1:5 and 1:50, or 1:5 and 1:10.

A textured surface can have a plurality of profile features having amixture of size dimensions within the nanometer to micrometer range(e.g., a portion of the profile features are on the nanometer scale anda portion of the profile features are on the micrometer scale). Atextured surface can have a plurality of profile features having amixture of dimensional ratios. The textured surface can have a profilefeature having one or more nanometer-scale projections or depressions ona micrometer-scale projection or depression.

The profile feature can have height and width dimensions that are withina factor of three of each other (0.33w≤h≤3w where w is the width and his the height of the profile feature) and/or height and lengthdimensions that are within a factor of three of each other (0.33l≤h≤3lwhere l is the length and h is the height of the profile feature). Theprofile feature can have a ratio of length:width that is from about 1:3to about 3:1, or about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1,or about 1:1.2 to about 1.2:1, or about 1:1. The width and length of theprofile features can be substantially the same or different.

The profile features can have a certain spatial arrangement. The spatialarrangement of the profile features may be uniform, such as spacedevenly apart or forming a pattern. The spatial arrangement can berandom. Adjacent profile features can be about 1 to 100 micrometersapart or about 5 to 100 micrometers apart. The desired spacing candepend, at least in part, on the size and/or shape of the profilesurfaces and the desired structural color effect.

The profile features can have a certain cross-sectional shape (withrespect to a plane parallel the first plane). The textured surface canhave a plurality of profile features having the same or similarcross-sectional shape. The textured surface has a plurality of profilefeatures having a mixture of different cross-sectional shapes. Thecross-sectional shapes of the profile features can include polygonal(e.g., square or triangle or rectangle cross section), circular,semi-circular, tubular, oval, random, high and low aspect ratios,overlapping profile features, and the like.

The profile feature (e.g., about 10 nanometers to 500 micrometers) caninclude an upper, convexly curved surface. The curved surface may extendsymmetrically either side of an uppermost point.

The profile feature can include protrusions from the textured surface.The profile feature can include indents (hollow areas) formed in thetextured surface. The profile feature can have a smooth, curved shape(e.g., a polygonal cross-section with curved corners).

The profile features (whether protrusions or depressions) can beapproximately conical or frusto-conical (i.e. the projections or indentsmay have horizontally or diagonally flattened tops) or have anapproximately part-spherical surface (e.g., a convex or concave surfacerespectively having a substantially even radius of curvature).

The profile features may have one or more sides or edges that extend ina direction that forms an angle to the first plane of the texturedsurface. The angle between the first plane and a side or edge of theprofile feature is about 45 degrees or less, about 30 degrees or less,about 25 degrees or less, or about 20 degrees or less. The one or moresides or edges may extend in a linear or planar orientation, or may becurved so that the angle changes as a function of distance from thefirst plane. The profile features may have one or more sides thatinclude step(s) and/or flat side(s). The profile feature can have one ormore sides (or portions thereof) that can be orthogonal or perpendicularto the first plane of the textured surface, or extend at an angle ofabout 10 degrees to 89 degrees to the first plane (90 degrees beingperpendicular or orthogonal to the first plane). The profile feature canhave a side with a stepped configuration, where portions of the side canbe parallel to the first plane of the textured surface or have an angleof about 1 degrees to 179 degrees (0 degrees being parallel to the firstplane).

The textured surface can have profile features with varying shapes(e.g., the profile features can vary in shape, height, width and lengthamong the profile features) or profile features with substantiallyuniform shapes and/or dimensions. The structural color produced by thetextured surface can be determined, at least in part, by the shape,dimensions, spacing, and the like, of the profile features.

The profile features can be shaped so as to result in a portion of thesurface (e.g., about 25 to 50 percent or more) being about normal to theincoming light when the light is incident at the normal to the firstplane of the textured surface. The profile features can be shaped so asto result in a portion of the surface (e.g., about 25 to 50 percent ormore) being about normal to the incoming light when the light isincident at an angle of up to 45 degrees to the first plane of thetextured surface.

The spatial orientation of the profile features on the textured surfaceis set to reduce distortion effects, e.g., caused by the interference ofone profile feature with another in regard to the structural color ofthe surface. Since the shape, dimension, relative orientation of theprofile features can vary considerably across the textured surface, thedesired spacing and/or relative positioning for a particular area (e.g.,in the micrometer range or about 1 to 10 square micrometers) havingprofile features can be appropriately determined. As discussed herein,the shape, dimension, relative orientation of the profile featuresaffect the contours of the optical layer, so the dimensions (e.g.,thickness), index of refraction, number of layers in the optical layerare considered when designing the textured side of the texture layer.

The profile features are located in nearly random positions relative toone another across a specific area of the textured surface (e.g., in themicrometer range or about 1 to 10 square micrometers to centimeter rangeor about 0.5 to 5 square centimeters, and all range increments therein),where the randomness does not defeat the purpose of producing thestructural color. In other words, the randomness is consistent with thespacing, shape, dimension, and relative orientation of the profilefeatures, the dimensions (e.g., thickness), index of refraction, andnumber of layers in the optical layer, and the like, with the goal toachieve the structural color.

The profile features are positioned in a set manner relative to oneanother across a specific area of the textured surface to achieve thepurpose of producing the structural color. The relative positions of theprofile features do not necessarily follow a pattern, but can follow apattern consistent with the desired structural color. As mentioned aboveand herein, various parameters related to the profile features, flatareas, and optical layer can be used to position the profile features ina set manner relative to one another.

The textured surface can include micro and/or nanoscale profile featuresthat can form gratings (e.g., a diffractive grating), photonic crystalstructure, a selective mirror structure, crystal fiber structures,deformed matrix structures, spiraled coiled structures, surface gratingstructures, and combinations thereof. The textured surface can includemicro and/or nanoscale profile features that form a grating having aperiodic or non-periodic design structure to produce the desiredstructural color. The micro and/or nanoscale profile features can have apeak-valley pattern of profile features and/or flat areas to produce thedesired structural color. The grading can be an Echelette grating.

The profile features and the flat areas of the textured surface in themulti-layer optical film can appear as topographical undulations in eachlayer of the optical layer. For example, referring to FIGS. 3A and 3B, amulti-layer optical film 200 includes a textured surface 220 having aplurality of profile features 222 and flat areas 224. As describedherein, one or more of the profile features 222 can be projections froma surface of the textured surface 220 (as shown in FIG. 3A), and/or oneor more of the profile features 222 can be depressions in a surface ofthe textured surface 220 (as shown in FIG. 3B). One or more opticallayers 240 are disposed on the side or surface of the textured surface220 having the profile features 222 and flat areas 224. In someembodiments, the resulting topography of the one or more optical layers240 is not identical to the topography of the textured surface 220, butrather, the one or more optical layers 240 can have elevated ordepressed regions 242 which are either elevated or depressed relative tothe height of the planar regions 244 and which roughly correspond to thelocation of the profile features 222 of the textured surface 220. Theone or more optical layers 240 also have planar regions 244 that roughlycorrespond to the location of the flat areas 224 of the textured surface220. Due to the presence of the elevated or depressed regions 242 andthe planar regions 244, the resultant overall topography of the opticallayer 240 can be that of an undulating or wave-like surface. Thedimension, shape, and spacing of the profile features along with thenumber of layers of the optical layer, the thickness of each of thelayers, refractive index of each layer, and the type of material, can beused to produce a multi-layer optical film which results in a particularstructural color.

Now having described the multi-layer optical film and the texturedsurface, additional details will be provided for the optionally presentprimer layer. The multi-layer optical film is used to produce thestructural color, where the multi-layer optical film can include (e.g.,as part of the multi-layer optical film) or use the primer layer toproduce the structural color. As described herein, the multi-layeroptical film can also include (e.g., as part of multi-layer opticalfilm) the optional textured surface, such as a texture layer and/or atextured surface. The combination of the multi-layer optical film andthe optional texture layer and the optional primer layer can form astructure having one of the following designs: texture layer/primerlayer/multi-layer optical film or primer layer/texture layer/multi-layeroptical film. The primer layer can have a thickness of about 3nanometers to 200 micrometers, or about 1 to about 200 micrometers, orabout 10 to about 100 micrometers, or about 10 to about 80 micrometers.The structure can include the combination of the primer layer, themulti-layer optical film, and (optionally) textured surface. Selectionof variables associated with the primer layer, texture layer, and themulti-layer optical film, can be used to control and select the desiredstructural color.

The structure can include the primer layer, the textured surface(optionally), and the multi-layer optical film (e.g., optical element orlayer), where the multi-layer optical film is disposed on the texturedsurface or the primer layer, depending upon the design. The combinationof the primer layer, the textured surface, and the multi-layer opticalfilm imparts structural color, to the bladder, where the structuralcolor is different than the primer color, optionally with or without theapplication of pigments or dyes to the bladder. The multi-layer opticalfilm can be disposed onto the primer layer and/or the textured surface.The primer layer can include the textured surface as described herein.For example, the primer layer can be formed in a way so that it has thetextured surface.

The primer layer can include a paint layer (e.g., dyes, pigments, and acombination thereof), an ink layer, a reground layer, an at leastpartially degraded polymer layer, a metal layer, an oxide layer, or acombination thereof. The primer layer can have a light or dark color.The primer layer can have a dark color. For example the dark color canbe selected from: black, shades of black, brown, dark shades of brown,dark shades of red, dark shades of orange, dark shades of yellow, darkshades of green, dark shades of cyan, dark shades of blue, dark shadesof violet, grey, dark shades of gray, dark shades of magenta, darkshades of indigo, tones, tints, shades, or hues of any of these, and acombination thereof. The color can be defined using the L*a*b system,where the value of L* can be about 70 or less, about 60 or less, about50 or less, about 40 or less, or about 30 or less and a* and b*coordinate values can vary across the positive and negative valuescales.

The primer layer can be formed using digital printing, inkjet printing,offset printing, pad printing, screen printing, flexographic printing,heat transfer printing, physical vapor deposition including: chemicalvapor deposition, pulsed laser deposition, evaporative deposition,sputtering deposition (radio frequency, direct current, reactive,non-reactive), plasma enhanced chemical vapor deposition, electron beamdeposition, cathodic arc deposition, low pressure chemical vapordeposition and wet chemistry techniques such as layer by layerdeposition, sol-gel deposition, or Langmuir-Blodgett. Alternatively orin addition, the primer layer can be applied by spray coating, dipcoating, brushing, spin coating, doctor blade coating, and the like.

The primer layer can have a percent transmittance of about 40% or less,about 30% or less, about 20% or less, about 15% or less, about 10% orless, about 5% or less, or about 1% or less, where “less” can includeabout 0% (e.g., 0 to 0.01 or 0 to 0.1), about 1%, about 2.5%, or about5%.

The paint layer can include a paint composition that, upon applying tothe bladder, forms a thin layer. The thin layer can be a solid filmhaving a dark color, such as those described above. The paint caninclude known paint compositions that can comprise one or more of thefollowing components: one or more paint resin, one or more polymers, oneor more dyes, and one or more pigments as well as water, film-formingsolvents, drying agents, thickeners, surfactants, anti-skinning agents,plasticizers, mildewcides, mar-resistant agents, anti-flooding agents,and combinations thereof.

The primer layer can comprise a reground, and at least partiallydegraded, polymer layer. The reground, and at least partially degraded,polymer layer can have a dark color, such as those described above.

The primer layer can include a metal layer or the oxide layer. The metallayer or the oxide layer can have a dark color, such as those describedabove. The oxide layer can be a metal oxide, a doped metal oxide, or acombination thereof. The metal layer, the metal oxide or the doped metaloxide can include the following: the transition metals, the metalloids,the lanthanides, and the actinides, as well as nitrides, oxynitrides,sulfides, sulfates, selenides, tellurides and a combination of these.The metal oxide can include titanium oxide, aluminum oxide, silicondioxide, tin dioxide, chromia, iron oxide, nickel oxide, silver oxide,cobalt oxide, zinc oxide, platinum oxide, palladium oxide, vanadiumoxide, molybdenum oxide, lead oxide, and combinations thereof as well asdoped versions of each. In some aspects, the primer layer can consistessentially of a metal oxide. In some aspects, the primer layer canconsist essentially of titanium dioxide or silicon dioxide. In someaspects, the primer layer can consist essentially of titanium dioxide.The metal oxide can be doped with water, inert gasses (e.g., argon),reactive gasses (e.g., oxygen or nitrogen), metals, small molecules, anda combination thereof. In some aspects, the primer layer can consistessentially of a doped metal oxide or a doped metal oxynitride or both.

The primer layer can be a coating on the surface of the bladder. Thecoating can be chemically bonded (e.g., covalently bonded, ionicallybonded, hydrogen bonded, and the like) to the surface of the bladder.The coating has been found to bond well to a surface made of a polymericmaterial. In an example, the surface of the bladder can be made of apolymeric material such as a polyurethane, including a thermoplasticpolyurethane (TPU), as those described herein.

The coating can be a crosslinked coating that includes one or morecolorants such as solid pigment particles or dye. The crosslinkedcoating can be a matrix of crosslinked polymers (e.g., a crosslinkedpolyester polyurethane polymer or copolymer). The colorants can beentrapped in the coating, including entrapped in the matrix ofcrosslinked polymers. The solid pigment particles or dye can bephysically entrapped in the crosslinked polymer matrix, can bechemically bonded (e.g., covalently bonded, ionically bonded, hydrogenbonded, and the like, with the coating including the polymeric matrix orwith the material forming the surface of the bladder to which thecoating is applied), or a combination of physically bonded andchemically bonded with the coating or bladder. The crosslinked coatingcan have a thickness of about 0.01 micrometers to 1000 micrometers.

The coating can be a product (or also referred to as “crosslinkedproduct”) of crosslinking a polymeric coating composition. The polymericcoating composition can include one or more colorants (e.g., solidpigment particles or dye) in a dispersion of polymers. The dispersion ofpolymers can include a water-borne dispersion of polymers such as awater-borne dispersion of polyurethane polymers, including polyesterpolyurethane copolymers). The water-borne dispersion of polymers can becrosslinked to entrap the colorants. The colorants can be physicallyentrapped in the crosslinked product, can be chemically bonded (e.g.,covalently bonded, ionically bonded, hydrogen bonded, and the like, withthe crosslinked copolymer matrix), or can be both physically bonded andchemically bonded with the crosslinked product. The product can beformed by crosslinking the polymeric coating composition. The productcan have a thickness of about 0.01 micrometer to 1000 micrometers.

The coating can include colorants such a pigment (e.g., a solid pigmentparticle) or a dye. The solid pigment particles can include inorganicpigments such as metal and metal oxides such as homogeneous inorganicpigments, core-shell pigments and the like, as well as carbon pigments(e.g., carbon black), clay earth pigments, and ultramarine pigments. Thesolid pigment particles can be biological or organic pigments. The solidpigment particles can be of a type known in the art as an extenderpigment, which include, but are not limited to, calcium carbonate,calcium silicate, mica, clay, silica, barium sulfate and the like. Theamount of the solid pigment particles sufficient to achieve the desiredcolor intensity, shade, and opacity, can be in amounts up to about 5percent to 25 percent or more by weight of the coating. The pigments caninclude those sold by KP Pigments such as pearl pigments, color shiftpigments (e.g., CALYPSO, JEDI, VERO, BLACKHOLE, LYNX, ROSE GOLD, and thelike), hypershift pigments, interference pigments and the like.

The colorant can be a dye such as an anionic dye, a cationic dye, adirect dye, a metal complex dye, a basic dye, a disperse dye, a solventdye, a polymeric dye, a polymeric dye colorant, or a nonionic dye, wherethe coating can include one or more dyes and/or types of dyes. The dyecan be a water-miscible dye. The dye can be a solubilized dye. Theanionic dye can be an acid dye. The dye can be applied separately fromthe coating (e.g., either before or after the coating is applied and/orcured).

Acid dyes are water-soluble anionic dyes. Acid dyes are available in awide variety, from dull tones to brilliant shades. Chemically, acid dyesinclude azo, anthraquinone and triarylmethane compounds. The “ColorIndex” (C.I.), published jointly by the Society of Dyers and Colourists(UK) and by the American Association of Textile Chemists and Colorists(USA), is the most extensive compendium of dyes and pigments for largescale coloration purposes, including 12000 products under 2000 C.I.generic names. In the C.I. each compound is presented with two numbersreferring to the coloristic and chemical classification. The “genericname” refers to the field of application and/or method of coloration,while the other number is the “constitution number.” Examples of aciddyes include Acid Yellow 1, 17, 23, 25, 34, 42, 44, 49, 61, 79, 99, 110,116, 127, 151, 158:1, 159, 166, 169, 194, 199, 204, 220, 232, 241, 246,and 250; Acid Red, 1, 14, 17, 18, 42, 57, 88, 97, 118, 119, 151, 183,184, 186, 194, 195, 198, 211, 225, 226, 249, 251, 257, 260, 266, 278,283, 315, 336, 337, 357, 359, 361, 362, 374, 405, 407, 414, 418, 419,and 447; Acid Violet 3, 5, 7, 17, 54, 90, and 92; Acid Brown 4, 14, 15,45, 50, 58, 75, 97, 98, 147, 160:1, 161, 165, 191, 235, 239, 248, 282,283, 289, 298, 322, 343, 349, 354, 355, 357, 365, 384, 392, 402, 414,420, 422, 425, 432, and 434; Acid Orange 3, 7, 10, 19, 33, 56, 60, 61,67, 74, 80, 86, 94, 139, 142, 144, 154, and 162; Acid Blue 1, 7, 9, 15,92, 133, 158, 185, 193, 277, 277:1, 314, 324, 335, and 342; Acid Green1, 12, 68:1, 73, 80, 104, 114, and 119; Acid Black 1, 26, 52, 58, 60,64, 65, 71, 82, 84, 107, 164, 172, 187, 194, 207, 210, 234, 235, andcombinations of these. The acid dyes may be used singly or in anycombination in the ink composition.

Acid dyes and nonionic disperse dyes are commercially available frommany sources, including Dystar L.P., Charlotte, N.C. under the tradenameTELON, Huntsman Corporation, Woodlands, Tex., USA under the tradenameERIONYL and TECTILON, BASF SE, Ludwigshafen, Germany under the tradenameBASACID, and Bezema AG, Montlingen, Switzerland under the tradenameBemacid.

The colorant can include the dye and a quaternary (tetraalkyl) ammoniumsalt, in particular when the dye is acidic dye. The quaternary(tetraalkyl) ammonium salt can react with the dye (e.g., acid dye) toform a complexed dye that can be used in the coating. The “alkyl” groupcan include C1 to C10 alkyl groups. The quaternary (tetraalkyl) ammoniumsalt can be selected from soluble tetrabutylammonium compounds andtetrahexylammonium compounds. The counterion of the quaternary ammoniumsalt should be selected so that the quaternary ammonium salt forms astable solution with the dye (e.g., anionic dye). The quaternaryammonium compound may be, for example, a halide (such as chloride,bromide or iodide), hydroxide, sulfate, sulfite, carbonate, perchlorate,chlorate, bromate, iodate, nitrate, nitrite, phosphate, phosphite,hexfluorophosphite, borate, tetrafluoroborate, cyanide, isocyanide,azide, thiosulfate, thiocyanate, or carbon/late (such as acetate oroxalate). The tetraalkylammonium compound can be or include atetrabutylammonium halide or tetrahexylammonium halide, particularly atetrabutylammonium bromide or chloride or a tetrahexylammonium bromideor chloride. The coating (e.g., coating, polymeric coating composition(prior to curing) can include about 1 to 15 weight percent of thequaternary ammonium salt. The molar ratio of the acid dye to thequaternary ammonium compound can range from about 3:1 to 1:3 or about1.5:1 to 1:1.5.

The coating (e.g., coating, polymeric coating composition (prior tocuring), monomers and/or polymers of the matrix of crosslinked polymers,or precursors of the coating) can include a cross-linker, whichfunctions to crosslink the polymeric components of the coating. Thecross-linker can be a water-borne cross-linker. The cross-linker caninclude one or more of the following: a polycarboxylic acid crosslinkingagent, an aldehyde crosslinking agent, a polyisocyanate crosslinkingagent, or a combination thereof. The polycarboxylic acid crosslinkingagent can be a polycarboxylic acid having from 2 to 9 carbon atoms. Forexample, the cross-linker can include a polyacrylic acid, a polymaleicacid, a copolymer of acid, a copolymer of maleic acid, fumaric acid, or1, 2, 3, 4-butanetetracarboxylic acid. The concentration of thecross-linker can be about 0.01 to 5 weight percent or 1 to 3 weightpercent of the coating.

The coating (e.g., coating, polymeric coating composition (prior tocuring), monomers and/or polymers of the matrix of crosslinked polymers,or precursors of the coating) can include a solvent. The solvent can bean organic solvent. The organic solvent can be a water-miscible organicsolvent. The coating may not include water, or may be essentially freeof water. For example, the solvent can be or includes acetone, ethanol,2-propanol, ethyl acetate, isopropyl acetate, methanol, methyl ethylketone, 1-butanol, t-butanol, or any mixture thereof.

Additional details are provided regarding the polymeric materialsreferenced herein for example, the polymers described in reference tothe bladder, components of the bladder, article, structure, layer, film,foam, primer layer, coating, and the like. The polymer can be athermoset polymer or a thermoplastic polymer. The polymer can be anelastomeric polymer, including an elastomeric thermoset polymer or anelastomeric thermoplastic polymer. The polymer can be selected from:polyurethanes (including elastomeric polyurethanes, thermoplasticpolyurethanes (TPUs), and elastomeric TPUs), polyesters, polyethers,polyamides, vinyl polymers (e.g., copolymers of vinyl alcohol, vinylesters, ethylene, acrylates, methacrylates, styrene, and so on),polyacrylonitriles, polyphenylene ethers, polycarbonates, polyureas,polystyrenes, co-polymers thereof (including polyester-polyurethanes,polyether-polyurethanes, polycarbonate-polyurethanes, polyether blockpolyamides (PEBAs), and styrene block copolymers), and any combinationthereof, as described herein. The polymer can include one or morepolymers selected from the group consisting of polyesters, polyethers,polyamides, polyurethanes, polyolefins copolymers of each, andcombinations thereof.

The term “polymer” refers to a chemical compound formed of a pluralityof repeating structural units referred to as monomers. Polymers oftenare formed by a polymerization reaction in which the plurality ofstructural units become covalently bonded together. When the monomerunits forming the polymer all have the same chemical structure, thepolymer is a homopolymer. When the polymer includes two or more monomerunits having different chemical structures, the polymer is a copolymer.One example of a type of copolymer is a terpolymer, which includes threedifferent types of monomer units. The co-polymer can include two or moredifferent monomers randomly distributed in the polymer (e.g., a randomco-polymer). Alternatively, one or more blocks containing a plurality ofa first type of monomer can be bonded to one or more blocks containing aplurality of a second type of monomer, forming a block copolymer. Asingle monomer unit can include one or more different chemicalfunctional groups.

Polymers having repeating units which include two or more types ofchemical functional groups can be referred to as having two or moresegments. For example, a polymer having repeating units of the samechemical structure can be referred to as having repeating segments.Segments are commonly described as being relatively harder or softerbased on their chemical structures, and it is common for polymers toinclude relatively harder segments and relatively softer segments bondedto each other in a single monomeric unit or in different monomericunits. When the polymer includes repeating segments, physicalinteractions or chemical bonds can be present within the segments orbetween the segments or both within and between the segments. Examplesof segments often referred to as hard segments include segmentsincluding a urethane linkage, which can be formed from reacting anisocyanate with a polyol to form a polyurethane. Examples of segmentsoften referred to as soft segments include segments including an alkoxyfunctional group, such as segments including ether or ester functionalgroups, and polyester segments. Segments can be referred to based on thename of the functional group present in the segment (e.g., a polyethersegment, a polyester segment), as well as based on the name of thechemical structure which was reacted in order to form the segment (e.g.,a polyol-derived segment, an isocyanate-derived segment). When referringto segments of a particular functional group or of a particular chemicalstructure from which the segment was derived, it is understood that thepolymer can contain up to 10 mole percent of segments of otherfunctional groups or derived from other chemical structures. Forexample, as used herein, a polyether segment is understood to include upto 10 mole percent of non-polyether segments.

As previously described, the polymer can be a thermoplastic polymer. Ingeneral, a thermoplastic polymer softens or melts when heated andreturns to a solid state when cooled. The thermoplastic polymertransitions from a solid state to a softened state when its temperatureis increased to a temperature at or above its softening temperature, anda liquid state when its temperature is increased to a temperature at orabove its melting temperature. When sufficiently cooled, thethermoplastic polymer transitions from the softened or liquid state tothe solid state. As such, the thermoplastic polymer may be softened ormelted, molded, cooled, re-softened or re-melted, re-molded, and cooledagain through multiple cycles. For amorphous thermoplastic polymers, thesolid state is understood to be the “rubbery” state above the glasstransition temperature of the polymer. The thermoplastic polymer canhave a melting temperature from about 90 degrees C. to about 190 degreesC. when determined in accordance with ASTM D3418-97 as described hereinbelow, and includes all subranges therein in increments of 1 degree. Thethermoplastic polymer can have a melting temperature from about 93degrees C. to about 99 degrees C. when determined in accordance withASTM D3418-97 as described herein below. The thermoplastic polymer canhave a melting temperature from about 112 degrees C. to about 118degrees C. when determined in accordance with ASTM D3418-97 as describedherein below.

The glass transition temperature is the temperature at which anamorphous polymer transitions from a relatively brittle “glassy” stateto a relatively more flexible “rubbery” state. The thermoplastic polymercan have a glass transition temperature from about −20 degrees C. toabout 30 degrees C. when determined in accordance with ASTM D3418-97 asdescribed herein below. The thermoplastic polymer can have a glasstransition temperature (from about −13 degree C. to about −7 degrees C.when determined in accordance with ASTM D3418-97 as described hereinbelow. The thermoplastic polymer can have a glass transition temperaturefrom about 17 degrees C. to about 23 degrees C. when determined inaccordance with ASTM D3418-97 as described herein below.

The thermoplastic polymer can have a melt flow index from about 10 toabout 30 cubic centimeters per 10 minutes (cm³/10 min) when tested inaccordance with ASTM D1238-13 as described herein below at 160 degreesC. using a weight of 2.16 kilograms (kg). The thermoplastic polymer canhave a melt flow index from about 22 cm³/10 min to about 28 cm³/10 minwhen tested in accordance with ASTM D1238-13 as described herein belowat 160 degrees C. using a weight of 2.16 kg.

The thermoplastic polymer can have a cold Ross flex test result of about120,000 to about 180,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below. Thethermoplastic polymer can have a cold Ross flex test result of about140,000 to about 160,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below.

The thermoplastic polymer can have a modulus from about 5 megaPascals(MPa) to about 100 MPa when determined on a thermoformed plaque inaccordance with ASTM D412-98 Standard Test Methods for Vulcanized Rubberand Thermoplastic Rubbers and Thermoplastic Elastomers-Tension withmodifications described herein below. The thermoplastic polymer can havea modulus from about 20 MPa to about 80 MPa when determined on athermoformed plaque in accordance with ASTM D412-98 Standard TestMethods for Vulcanized Rubber and Thermoplastic Rubbers andThermoplastic Elastomers-Tension with modifications described hereinbelow.

The polymer can be a thermoset polymer. As used herein, a “thermosetpolymer” is understood to refer to a polymer which cannot be heated andmelted, as its melting temperature is at or above its decompositiontemperature. A “thermoset material” refers to a material which comprisesat least one thermoset polymer. The thermoset polymer and/or thermosetmaterial can be prepared from a precursor (e.g., an uncured or partiallycured polymer or material) using thermal energy and/or actinic radiation(e.g., ultraviolet radiation, visible radiation, high energy radiation,infrared radiation) to form a partially cured or fully cured polymer ormaterial which no longer remains fully thermoplastic. In some cases, thecured or partially cured polymer or material may remain thermoelasticproperties, in that it is possible to partially soften and mold thepolymer or material at elevated temperatures and/or pressures, but it isnot possible to melt the polymer or material. The curing can bepromoted, for example, with the use of high pressure and/or a catalyst.In many examples, the curing process is irreversible since it results incross-linking and/or polymerization reactions of the precursors. Theuncured or partially cured polymers or materials can be malleable orliquid prior to curing. In some cases, the uncured or partially curedpolymers or materials can be molded into their final shape, or used asadhesives. Once hardened, a thermoset polymer or material cannot bere-melted in order to be reshaped. The textured surface can be formed bypartially or fully curing an uncured precursor material to lock in thetextured surface of the textured structure.

Polyurethane

The polymer can be a polyurethane, such as a thermoplastic polyurethane(also referred to as “TPU”). Alternatively, the polymer can be athermoset polyurethane. Additionally, polyurethane can be an elastomericpolyurethane, including an elastomeric TPU or an elastomeric thermosetpolyurethane. The elastomeric polyurethane can include hard and softsegments. The hard segments can comprise or consist of urethane segments(e.g., isocyanate-derived segments). The soft segments can comprise orconsist of alkoxy segments (e.g., polyol-derived segments includingpolyether segments, or polyester segments, or a combination of polyethersegments and polyester segments). The polyurethane can comprise orconsist essentially of an elastomeric polyurethane having repeating hardsegments and repeating soft segments.

One or more of the polyurethanes can be produced by polymerizing one ormore isocyanates with one or more polyols to produce polymer chainshaving carbamate linkages (—N(CO)O—) as illustrated below in Formula 1,where the isocyanate(s) each preferably include two or more isocyanate(—NCO) groups per molecule, such as 2, 3, or 4 isocyanate groups permolecule (although, mono-functional isocyanates can also be optionallyincluded, e.g., as chain terminating units).

Each R₁ group and R₂ group independently is an aliphatic or aromaticgroup. Optionally, each R₂ can be a relatively hydrophilic group,including a group having one or more hydroxyl groups.

Additionally, the isocyanates can also be chain extended with one ormore chain extenders to bridge two or more isocyanates, increasing thelength of the hard segment. This can produce polyurethane polymer chainsas illustrated below in Formula 2, where R₃ includes the chain extender.As with each R₁ and R₃, each R₃ independently is an aliphatic oraromatic functional group.

Each R₁ group in Formulas 1 and 2 can independently include a linear orbranched group having from 3 to 30 carbon atoms, based on the particularisocyanate(s) used, and can be aliphatic, aromatic, or include acombination of aliphatic portions(s) and aromatic portion(s). The term“aliphatic” refers to a saturated or unsaturated organic molecule orportion of a molecule that does not include a cyclically conjugated ringsystem having delocalized pi electrons. In comparison, the term“aromatic” refers to an organic molecule or portion of a molecule havinga cyclically conjugated ring system with delocalized pi electrons, whichexhibits greater stability than a hypothetical ring system havinglocalized pi electrons.

Each R₁ group can be present in an amount of about 5 percent to about 85percent by weight, from about 5 percent to about 70 percent by weight,or from about 10 percent to about 50 percent by weight, based on thetotal weight of the reactant compounds or monomers which form thepolymer.

In aliphatic embodiments (from aliphatic isocyanate(s)), each R₁ groupcan include a linear aliphatic group, a branched aliphatic group, acycloaliphatic group, or combinations thereof. For instance, each R₁group can include a linear or branched alkylene group having from 3 to20 carbon atoms (e.g., an alkylene having from 4 to 15 carbon atoms, oran alkylene having from 6 to 10 carbon atoms), one or more cycloalkylenegroups having from 3 to 8 carbon atoms (e.g., cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl), and combinationsthereof. The term “alkene” or “alkylene” as used herein refers to abivalent hydrocarbon. When used in association with the term C_(n) itmeans the alkene or alkylene group has “n” carbon atoms. For example,C₁₋₆ alkylene refers to an alkylene group having, e.g., 1, 2, 3, 4, 5,or 6 carbon atoms.

Examples of suitable aliphatic diisocyanates for producing thepolyurethane polymer chains include hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), butylenediisocyanate (BDI),bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylenediisocyanate (TMDI), bisisocyanatomethylcyclohexane,bisisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI),cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate(H12MDI), diisocyanatododecane, lysine diisocyanate, and combinationsthereof.

The isocyanate-derived segments can include segments derived fromaliphatic diisocyanate. A majority of the isocyanate-derived segmentscan comprise segments derived from aliphatic diisocyanates. At least 90%of the isocyanate-derived segments are derived from aliphaticdiisocyanates. The isocyanate-derived segments can consist essentiallyof segments derived from aliphatic diisocyanates. The aliphaticdiisocyanate-derived segments can be derived substantially (e.g., about50 percent or more, about 60 percent or more, about 70 percent or more,about 80 percent or more, about 90 percent or more) from linearaliphatic diisocyanates. At least 80% of the aliphaticdiisocyanate-derived segments can be derived from aliphaticdiisocyanates that are free of side chains. The segments derived fromaliphatic diisocyanates can include linear aliphatic diisocyanateshaving from 2 to 10 carbon atoms.

When the isocyanate-derived segments are derived from aromaticisocyanate(s)), each R₁ group can include one or more aromatic groups,such as phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl,biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl. Unlessotherwise indicated, an aromatic group can be an unsubstituted aromaticgroup or a substituted aromatic group, and can also includeheteroaromatic groups. “Heteroaromatic” refers to monocyclic orpolycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ringsystems, where one to four ring atoms are selected from oxygen,nitrogen, or sulfur, and the remaining ring atoms are carbon, and wherethe ring system is joined to the remainder of the molecule by any of thering atoms. Examples of suitable heteroaryl groups include pyridyl,pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl,tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, furanyl,quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl, andbenzothiazolyl groups.

Examples of suitable aromatic diisocyanates for producing thepolyurethane polymer chains include toluene diisocyanate (TDI), TDIadducts with trimethyloylpropane (TMP), methylene diphenyl diisocyanate(MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate(TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate,para-phenylene diisocyanate (PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4′-dibenzyl diisocyanate (DBDI),4-chloro-1,3-phenylene diisocyanate, and combinations thereof. Thepolymer chains can be substantially free of aromatic groups.

The polyurethane polymer chains can be produced from diisocyanatesincluding HMDI, TDI, MDI, H₁₂ aliphatics, and combinations thereof. Forexample, the polyurethane can comprise one or more polyurethane polymerchains produced from diisocyanates including HMDI, TDI, MDI, H₁₂aliphatics, and combinations thereof.

Polyurethane chains which are at least partially crosslinked or whichcan be crosslinked, can be used in accordance with the presentdisclosure. It is possible to produce crosslinked or crosslinkablepolyurethane chains by reacting multi-functional isocyanates to form thepolyurethane. Examples of suitable triisocyanates for producing thepolyurethane chains include TDI, HDI, and IPDI adducts withtrimethyloylpropane (TMP), uretdiones (i.e., dimerized isocyanates),polymeric MDI, and combinations thereof.

The R₃ group in Formula 2 can include a linear or branched group havingfrom 2 to 10 carbon atoms, based on the particular chain extender polyolused, and can be, for example, aliphatic, aromatic, or an ether orpolyether. Examples of suitable chain extender polyols for producing thepolyurethane include ethylene glycol, lower oligomers of ethylene glycol(e.g., diethylene glycol, triethylene glycol, and tetraethylene glycol),1,2-propylene glycol, 1,3-propylene glycol, lower oligomers of propyleneglycol (e.g., dipropylene glycol, tripropylene glycol, andtetrapropylene glycol), 1,4-butylene glycol, 2,3-butylene glycol,1,6-hexanediol, 1,8-octanediol, neopentyl glycol,1,4-cyclohexanedimethanol, 2-ethyl-1,6-hexanediol,1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, dihydroxyalkylatedaromatic compounds (e.g., bis(2-hydroxyethyl) ethers of hydroquinone andresorcinol, xylene-a,a-diols, bis(2-hydroxyethyl) ethers ofxylene-a,a-diols, and combinations thereof.

The R₂ group in Formula 1 and 2 can include a polyether group, apolyester group, a polycarbonate group, an aliphatic group, or anaromatic group. Each R₂ group can be present in an amount of about 5percent to about 85 percent by weight, from about 5 percent to about 70percent by weight, or from about 10 percent to about 50 percent byweight, based on the total weight of the reactant monomers.

At least one R₂ group of the polyurethane includes a polyether segment(i.e., a segment having one or more ether groups). Suitable polyethergroups include, but are not limited to, polyethylene oxide (PEO),polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof. The term“alkyl” as used herein refers to straight chained and branched saturatedhydrocarbon groups containing one to thirty carbon atoms, for example,one to twenty carbon atoms, or one to ten carbon atoms. When used inassociation with the term C_(n) it means the alkyl group has “n” carbonatoms. For example, C₄ alkyl refers to an alkyl group that has 4 carbonatoms. C₁₋₇ alkyl refers to an alkyl group having a number of carbonatoms encompassing the entire range (i.e., 1 to 7 carbon atoms), as wellas all subgroups (e.g., 1-6, 2-7, 1-5, 3-6, 1, 2, 3, 4, 5, 6, and 7carbon atoms). Non-limiting examples of alkyl groups include, methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl(1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unlessotherwise indicated, an alkyl group can be an unsubstituted alkyl groupor a substituted alkyl group.

In some examples of the polyurethane, the at least one R₂ group includesa polyester group. The polyester group can be derived from thepolyesterification of one or more dihydric alcohols (e.g., ethyleneglycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol,1,3-butanediol, 2-methylpentanediol, 1,5-diethylene glycol,1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol,cyclohexanedimethanol, and combinations thereof) with one or moredicarboxylic acids (e.g., adipic acid, succinic acid, sebacic acid,suberic acid, methyladipic acid, glutaric acid, pimelic acid, azelaicacid, thiodipropionic acid and citraconic acid and combinationsthereof). The polyester group also can be derived from polycarbonateprepolymers, such as poly(hexamethylene carbonate) glycol,poly(propylene carbonate) glycol, poly(tetramethylene carbonate)glycol,and poly(nonanemethylene carbonate) glycol. Suitable polyesters caninclude, for example, polyethylene adipate (PEA), poly(1,4-butyleneadipate), poly(tetramethylene adipate), poly(hexamethylene adipate),polycaprolactone, polyhexamethylene carbonate, poly(propylenecarbonate), poly(tetramethylene carbonate), poly(nonanemethylenecarbonate), and combinations thereof.

At least one R₂ group can include a polycarbonate group. Thepolycarbonate group can be derived from the reaction of one or moredihydric alcohols (e.g., ethylene glycol, 1,3-propylene glycol,1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol,2-methylpentanediol 1,5-diethylene glycol, 1,5-pentanediol,1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, andcombinations thereof) with ethylene carbonate.

The aliphatic group can be linear and can include, for example, analkylene chain having from 1 to 20 carbon atoms or an alkenylene chainhaving from 1 to 20 carbon atoms (e.g., methylene, ethylene, propylene,butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, tridecylene, ethenylene, propenylene,butenylene, pentenylene, hexenylene, heptenylene, octenylene,nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). Theterm “alkene” or “alkylene” refers to a bivalent hydrocarbon. The term“alkenylene” refers to a bivalent hydrocarbon molecule or portion of amolecule having at least one double bond.

The aliphatic and aromatic groups can be substituted with one or morependant relatively hydrophilic and/or charged groups. The pendanthydrophilic group can include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9,10 or more) hydroxyl groups. The pendant hydrophilic group includes oneor more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) amino groups. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) carboxylate groups. For example, thealiphatic group can include one or more polyacrylic acid group. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) sulfonate groups. In some cases, thependant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7,8, 9, 10 or more) phosphate groups. In some examples, the pendanthydrophilic group includes one or more ammonium groups (e.g., tertiaryand/or quaternary ammonium). In other examples, the pendant hydrophilicgroup includes one or more zwitterionic groups (e.g., a betaine, such aspoly(carboxybetaine (pCB) and ammonium phosphonate groups such as aphosphatidylcholine group).

The R₂ group can include charged groups that are capable of binding to acounterion to ionically crosslink the polymer and form ionomers. Forexample, R₂ is an aliphatic or aromatic group having pendant amino,carbon/late, sulfonate, phosphate, ammonium, or zwitterionic groups, orcombinations thereof.

When a pendant hydrophilic group is present, the pendant hydrophilicgroup can be at least one polyether group, such as two polyether groups.In other cases, the pendant hydrophilic group is at least one polyester.The pendant hydrophilic group can be a polylactone group (e.g.,polyvinylpyrrolidone). Each carbon atom of the pendant hydrophilic groupcan optionally be substituted with, e.g., an alkyl group having from 1to 6 carbon atoms. The aliphatic and aromatic groups can be graftpolymeric groups, wherein the pendant groups are homopolymeric groups(e.g., polyether groups, polyester groups, polyvinylpyrrolidone groups).

The pendant hydrophilic group can be a polyether group (e.g., apolyethylene oxide (PEO) group, a polyethylene glycol (PEG) group), apolyvinylpyrrolidone group, a polyacrylic acid group, or combinationsthereof.

The pendant hydrophilic group can be bonded to the aliphatic group oraromatic group through a linker. The linker can be any bifunctionalsmall molecule (e.g., one having from 1 to 20 carbon atoms) capable oflinking the pendant hydrophilic group to the aliphatic or aromaticgroup. For example, the linker can include a diisocyanate group, aspreviously described herein, which when linked to the pendanthydrophilic group and to the aliphatic or aromatic group forms acarbamate bond. The linker can be 4,4′-diphenylmethane diisocyanate(MDI), as shown below.

The pendant hydrophilic group can be a polyethylene oxide group and thelinking group can be MDI, as shown below.

The pendant hydrophilic group can be functionalized to enable it to bondto the aliphatic or aromatic group, optionally through the linker. Forexample, when the pendant hydrophilic group includes an alkene group,which can undergo a Michael addition with a sulfhydryl-containingbifunctional molecule (i.e., a molecule having a second reactive group,such as a hydroxyl group or amino group), resulting in a hydrophilicgroup that can react with the polymer backbone, optionally through thelinker, using the second reactive group. For example, when the pendanthydrophilic group is a polyvinylpyrrolidone group, it can react with thesulfhydryl group on mercaptoethanol to result in hydroxyl-functionalizedpolyvinylpyrrolidone, as shown below.

At least one R₂ group in the polyurethane can include apolytetramethylene oxide group. At least one R₂ group of thepolyurethane can include an aliphatic polyol group functionalized with apolyethylene oxide group or polyvinylpyrrolidone group, such as thepolyols described in E.P. Patent No. 2 462 908, which is herebyincorporated by reference. For example, the R₂ group can be derived fromthe reaction product of a polyol (e.g., pentaerythritol or2,2,3-trihydroxypropanol) and either MDI-derivatized methoxypolyethyleneglycol (to obtain compounds as shown in Formulas 6 or 7) or withMDI-derivatized polyvinylpyrrolidone (to obtain compounds as shown inFormulas 8 or 9) that had been previously been reacted withmercaptoethanol, as shown below.

At least one R₂ of the polyurethane can be a polysiloxane, In thesecases, the R₂ group can be derived from a silicone monomer of Formula10, such as a silicone monomer disclosed in U.S. Pat. No. 5,969,076,which is hereby incorporated by reference:

wherein: a is 1 to 10 or larger (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or10); each R₄ independently is hydrogen, an alkyl group having from 1 to18 carbon atoms, an alkenyl group having from 2 to 18 carbon atoms,aryl, or polyether; and each R₅ independently is an alkylene grouphaving from 1 to 10 carbon atoms, polyether, or polyurethane.

Each R₄ group can independently be a H, an alkyl group having from 1 to10 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, anaryl group having from 1 to 6 carbon atoms, polyethylene, polypropylene,or polybutylene group. Each R₄ group can independently be selected fromthe group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, s-butyl, t-butyl, ethenyl, propenyl, phenyl, and polyethylenegroups.

Each R₅ group can independently include an alkylene group having from 1to 10 carbon atoms (e.g., a methylene, ethylene, propylene, butylene,pentylene, hexylene, heptylene, octylene, nonylene, or decylene group).Each R₅ group can be a polyether group (e.g., a polyethylene,polypropylene, or polybutylene group). Each R₅ group can be apolyurethane group.

Optionally, the polyurethane can include an at least partiallycrosslinked polymeric network that includes polymer chains that arederivatives of polyurethane. The level of crosslinking can be such thatthe polyurethane retains thermoplastic properties (i.e., the crosslinkedthermoplastic polyurethane can be melted and re-solidified under theprocessing conditions described herein). The crosslinked polyurethanecan be a thermoset polymer. This crosslinked polymeric network can beproduced by polymerizing one or more isocyanates with one or morepolyamino compounds, polysulfhydryl compounds, or combinations thereof,as shown in Formulas 11 and 12, below:

wherein the variables are as described above. Additionally, theisocyanates can also be chain extended with one or more polyamino orpolythiol chain extenders to bridge two or more isocyanates, such aspreviously described for the polyurethanes of Formula 2.

The polyurethane chain can be physically crosslinked to anotherpolyurethane chain through e.g., nonpolar or polar interactions betweenthe urethane or carbamate groups of the polymers (the hard segments).The R₁ group in Formula 1, and the R₁ and R₃ groups in Formula 2, formthe portion of the polymer often referred to as the “hard segment”, andthe R₂ group forms the portion of the polymer often referred to as the“soft segment”. The soft segment is covalently bonded to the hardsegment. The polyurethane having physically crosslinked hard and softsegments can be a hydrophilic polyurethane (i.e., a polyurethane,including a thermoplastic polyurethane, including hydrophilic groups asdisclosed herein).

The polyurethane can be a thermoplastic polyurethane composed of MDI,PTMO, and 1,4-butylene glycol, as described in U.S. Pat. No. 4,523,005.Commercially available polyurethanes suitable for the present useinclude, but are not limited to those under the tradename “SANCURE”(e.g., the “SANCURE” series of polymer such as “SANCURE” 20025F) or“TECOPHILIC” (e.g., TG-500, TG-2000, SP-80A-150, SP-93A-100, SP-60D-60)(Lubrizol, Countryside, Ill., USA), “PELLETHANE” 2355-85ATP and2355-95AE (Dow Chemical Company of Midland, Mich., USA.), “ESTANE”(e.g., ALR G 500, or 58213; Lubrizol, Countryside, Ill., USA).

One or more of the polyurethanes (e.g., those used in the primer as thecoating (e.g., water-dispersible polyurethane)) can be produced bypolymerizing one or more isocyanates with one or more polyols to producecopolymer chains having carbamate linkages (—N(C═O)O—) and one or morewater-dispersible enhancing moieties, where the polymer chain includesone or more water-dispersible enhancing moieties (e.g., a monomer inpolymer chain). The water-dispersible polyurethane can also be referredto as “a water-borne polyurethane polymer dispersion.” Thewater-dispersible enhancing moiety can be added to the chain of Formula1 or 2 (e.g., within the chain and/or onto the chain as a side chain).Inclusion of the water-dispersible enhancing moiety enables theformation of a water-borne polyurethane dispersion. The term“water-borne” herein means the continuous phase of the dispersion orformulation of about 50 weight percent to 100 weight percent water,about 60 weight percent to 100 weight percent water, about 70 weightpercent to 100 weight percent water, or about 100 weight percent water.The term “water-borne dispersion” refers to a dispersion of a component(e.g., polymer, cross-linker, and the like) in water withoutco-solvents. The co-solvent can be used in the water-borne dispersionand the co-solvent can be an organic solvent. Additional detailregarding the polymers, polyurethanes, isocyantes and the polyols areprovided below.

The polyurethane (e.g., a water-borne polyurethane polymer dispersion)can include one or more water-dispersible enhancing moieties. Thewater-dispersible enhancing moiety can have at least one hydrophilic(e.g., poly(ethylene oxide)), ionic or potentially ionic group to assistdispersion of the polyurethane, thereby enhancing the stability of thedispersions. A water-dispersible polyurethane can be formed byincorporating a moiety bearing at least one hydrophilic group or a groupthat can be made hydrophilic (e.g., by chemical modifications such asneutralization) into the polymer chain. For example, these compounds canbe nonionic, anionic, cationic or zwitterionic or the combinationthereof. In one example, anionic groups such as carboxylic acid groupscan be incorporated into the chain in an inactive form and subsequentlyactivated by a salt-forming compound, such as a tertiary amine. Otherwater-dispersible enhancing moieties can also be reacted into thebackbone through urethane linkages or urea linkages, including lateralor terminal hydrophilic ethylene oxide or ureido units.

The water-dispersible enhancing moiety can be a one that includescarboxyl groups. Water-dispersible enhancing moiety that include acarboxyl group can be formed from hydroxy-carboxylic acids having thegeneral formula (H₀)_(x)Q(COOH)_(y), where Q can be a straight orbranched bivalent hydrocarbon radical containing 1 to 12 carbon atoms,and x and y can each independently be 1 to 3. Illustrative examplesinclude dimethylolpropanoic acid (DMPA), dimethylol butanoic acid(DMBA), citric acid, tartaric acid, glycolic acid, lactic acid, malicacid, dihydroxymalic acid, dihydroxytartaric acid, and the like, andmixtures thereof.

The water-dispersible enhancing moiety can include reactive polymericpolyol components that contain pendant anionic groups that can bepolymerized into the backbone to impart water dispersiblecharacteristics to the polyurethane. Anionic functional polymericpolyols can include anionic polyester polyols, anionic polyetherpolyols, and anionic polycarbonate polyols, where additional detail isprovided in U.S. Pat. No. 5,334,690.

The water-dispersible enhancing moiety can include a side chainhydrophilic monomer. For example, the water-dispersible enhancing moietyincluding the side chain hydrophilic monomer can include alkylene oxidepolymers and copolymers in which the alkylene oxide groups have from2-10 carbon atoms as shown in U.S. Pat. No. 6,897,281. Additional typesof water-dispersible enhancing moieties can include thioglycolic acid,2,6-dihydroxybenzoic acid, sulfoisophthalic acid, polyethylene glycol,and the like, and mixtures thereof. Additional details regardingwater-dispersible enhancing moieties can be found in U.S. Pat. No.7,476,705.

Polyamides

The polymer can comprise a polyamide, such as a thermoplastic polyamide,or a thermoset polyamide. The polyamide can be an elastomeric polyamide,including an elastomeric thermoplastic polyamide or an elastomericthermoset polyamide. The polyamide can be a polyamide homopolymer havingrepeating polyamide segments of the same chemical structure.Alternatively, the polyamide can comprise a number of polyamide segmentshaving different polyamide chemical structures (e.g., polyamide 6segments, polyamide 11 segments, polyamide 12 segments, polyamide 66segments, etc.). The polyamide segments having different chemicalstructure can be arranged randomly, or can be arranged as repeatingblocks.

The polyamide can be a co-polyamide (i.e., a co-polymer includingpolyamide segments and non-polyamide segments). The polyamide segmentsof the co-polyamide can comprise or consist of polyamide 6 segments,polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, orany combination thereof. The polyamide segments of the co-polyamide canbe arranged randomly, or can be arranged as repeating segments. Thepolyamide segments can comprise or consist of polyamide 6 segments, orpolyamide 12 segments, or both polyamide 6 segment and polyamide 12segments. In the example where the polyamide segments of theco-polyamide include of polyamide 6 segments and polyamide 12 segments,the segments can be arranged randomly. The non-polyamide segments of theco-polyamide can comprise or consist of polyether segments, polyestersegments, or both polyether segments and polyester segments. Theco-polyamide can be a block co-polyamide, or can be a randomco-polyamide. The copolyamide can be formed from the polycondensation ofa polyamide oligomer or prepolymer with a second oligomer prepolymer toform a copolyamide (i.e., a co-polymer including polyamide segments.Optionally, the second prepolymer can be a hydrophilic prepolymer.

The polyamide can be a polyamide-containing block co-polymer. Forexample, the block co-polymer can have repeating hard segments, andrepeating soft segments. The hard segments can comprise polyamidesegments, and the soft segments can comprise non-polyamide segments. Thepolyamide-containing block co-polymer can be an elastomeric co-polyamidecomprising or consisting of polyamide-containing block co-polymershaving repeating hard segments and repeating soft segments. In blockco-polymers, including block co-polymers having repeating hard segmentsand soft segments, physical crosslinks can be present within thesegments or between the segments or both within and between thesegments.

The polyamide itself, or the polyamide segment of thepolyamide-containing block co-polymer can be derived from thecondensation of polyamide prepolymers, such as lactams, amino acids,and/or diamino compounds with dicarboxylic acids, or activated formsthereof. The resulting polyamide segments include amide linkages(—(CO)NH—). The term “amino acid” refers to a molecule having at leastone amino group and at least one carboxyl group. Each polyamide segmentof the polyamide can be the same or different.

The polyamide or the polyamide segment of the polyamide-containing blockco-polymer can be derived from the polycondensation of lactams and/oramino acids, and can include an amide segment having a structure shownin Formula 13, below, wherein R₆ group represents the portion of thepolyamide derived from the lactam or amino acid.

The R₆ group can be derived from a lactam. The R₆ group can be derivedfrom a lactam group having from 3 to 20 carbon atoms, or a lactam grouphaving from 4 to 15 carbon atoms, or a lactam group having from 6 to 12carbon atoms. The R₆ group can be derived from caprolactam orlaurolactam. The R₆ group can be derived from one or more amino acids.The R₆ group can be derived from an amino acid group having from 4 to 25carbon atoms, or an amino acid group having from 5 to 20 carbon atoms,or an amino acid group having from 8 to 15 carbon atoms. The R₆ groupcan be derived from 12-aminolauric acid or 11-aminoundecanoic acid.

Optionally, in order to increase the relative degree of hydrophilicityof the polyamide-containing block co-polymer, Formula 13 can include apolyamide-polyether block copolymer segment, as shown below:

wherein m is 3-20, and n is 1-8. Optionally, m is 4-15, or 6-12 (e.g.,6, 7, 8, 9, 10, 11, or 12), and n is 1, 2, or 3. For example, m can be11 or 12, and n can be 1 or 3. The polyamide or the polyamide segment ofthe polyamide-containing block co-polymer can be derived from thecondensation of diamino compounds with dicarboxylic acids, or activatedforms thereof, and can include an amide segment having a structure shownin Formula 15, below, wherein the R₇ group represents the portion of thepolyamide derived from the diamino compound, and the R₈ group representsthe portion derived from the dicarboxylic acid compound:

The R₇ group can be derived from a diamino compound that includes analiphatic group having from 4 to 15 carbon atoms, or from 5 to 10 carbonatoms, or from 6 to 9 carbon atoms. The diamino compound can include anaromatic group, such as phenyl, naphthyl, xylyl, and tolyl. Suitablediamino compounds from which the R₇ group can be derived include, butare not limited to, hexamethylene diamine (HMD), tetramethylene diamine,trimethyl hexamethylene diamine (TMD), m-xylylene diamine (MXD), and1,5-pentamine diamine. The R₈ group can be derived from a dicarboxylicacid or activated form thereof, including an aliphatic group having from4 to 15 carbon atoms, or from 5 to 12 carbon atoms, or from 6 to 10carbon atoms. The dicarboxylic acid or activated form thereof from whichR₈ can be derived includes an aromatic group, such as phenyl, naphthyl,xylyl, and tolyl groups. Suitable carboxylic acids or activated formsthereof from which R₈ can be derived include adipic acid, sebacic acid,terephthalic acid, and isophthalic acid. The polyamide chain can besubstantially free of aromatic groups.

Each polyamide segment of the polyamide (including thepolyamide-containing block co-polymer) can be independently derived froma polyamide prepolymer selected from the group consisting of12-aminolauric acid, caprolactam, hexamethylene diamine and adipic acid.

The polyamide can comprise or consist essentially of apoly(ether-block-amide). The poly(ether-block-amide) can be formed fromthe polycondensation of a carboxylic acid terminated polyamideprepolymer and a hydroxyl terminated polyether prepolymer to form apoly(ether-block-amide), as shown in Formula 16:

The poly(ether block amide) polymer can be prepared by polycondensationof polyamide blocks containing reactive ends with polyether blockscontaining reactive ends. Examples include: 1) polyamide blockscontaining diamine chain ends with polyoxyalkylene blocks containingcarboxylic chain ends; 2) polyamide blocks containing dicarboxylic chainends with polyoxyalkylene blocks containing diamine chain ends obtainedby cyanoethylation and hydrogenation of aliphatic dihydroxylatedalpha-omega polyoxyalkylenes known as polyether diols; 3) polyamideblocks containing dicarboxylic chain ends with polyether diols, theproducts obtained in this particular case being polyetheresteramides.The polyamide block of the poly(ether-block-amide) can be derived fromlactams, amino acids, and/or diamino compounds with dicarboxylic acidsas previously described. The polyether block can be derived from one ormore polyethers selected from the group consisting of polyethylene oxide(PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks comprising dicarboxylic chain ends derived from thecondensation of α, ω-aminocarboxylic acids, of lactams or ofdicarboxylic acids and diamines in the presence of a chain-limitingdicarboxylic acid. In poly(ether block amide) polymers of this type, aα, ω-aminocarboxylic acid such as aminoundecanoic acid can be used; alactam such as caprolactam or lauryllactam can be used; a dicarboxylicacid such as adipic acid, decanedioic acid or dodecanedioic acid can beused; and a diamine such as hexamethylenediamine can be used; or variouscombinations of any of the foregoing. The copolymer can comprisepolyamide blocks comprising polyamide 12 or of polyamide 6.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of one or more α,ω-aminocarboxylic acids and/or of one or more lactams containing from 6to 12 carbon atoms in the presence of a dicarboxylic acid containingfrom 4 to 12 carbon atoms, and are of low mass, i.e., they have anumber-average molecular weight of from 400 to 1000. In poly(ether blockamide) polymers of this type, an α, ω-aminocarboxylic acid such asaminoundecanoic acid or aminododecanoic acid can be used; a dicarboxylicacid such as adipic acid, sebacic acid, isophthalic acid, butanedioicacid, 1,4-cyclohexyldicarboxylic acid, terephthalic acid, the sodium orlithium salt of sulphoisophthalic acid, dimerized fatty acids (thesedimerized fatty acids have a dimer content of at least 98 weight percentand are preferably hydrogenated) and dodecanedioic acidHOOC—(CH₂)₁₀—COOH can be used; and a lactam such as caprolactam andlauryllactam can be used; or various combinations of any of theforegoing. The copolymer can comprise polyamide blocks obtained bycondensation of lauryllactam in the presence of adipic acid ordodecanedioic acid and with a number average molecular weight of atleast 750 have a melting temperature of from about 127 to about 130degrees C. The various constituents of the polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., or from about 90 degrees C. to about 135 degrees C.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of at least one α,ω-aminocarboxylic acid (or a lactam), at least one diamine and at leastone dicarboxylic acid. In copolymers of this type, a α,ω-aminocarboxylicacid, the lactam and the dicarboxylic acid can be chosen from thosedescribed herein above and the diamine such as an aliphatic diaminecontaining from 6 to 12 atoms and can be acyclic and/or saturated cyclicsuch as, but not limited to, hexamethylenediamine, piperazine,1-aminoethylpiperazine, bisaminopropylpiperazine, tetramethylenediamine,octamethylene-diamine, decamethylenediamine, dodecamethylenediamine,1,5-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyols,isophoronediamine (IPD), methylpentamethylenediamine (MPDM),bis(aminocyclohexyl)methane (BACM) andbis(3-methyl-4-aminocyclohexyl)methane (BMACM) can be used.

The polyamide can be a thermoplastic polyamide and the constituents ofthe polyamide block and their proportion can be chosen in order toobtain a melting temperature of less than 150 degrees C., such as amelting point of from about 90 degrees C. to about 135 degrees C. Thevarious constituents of the thermoplastic polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., such as from about and 90 degrees C. to about 135degrees C.

The number average molar mass of the polyamide blocks can be from about300 grams per mole to about 15,000 grams per mole, from about 500 gramsper mole to about 10,000 grams per mole, from about 500 grams per moleto about 6,000 grams per mole, from about 500 grams per mole to about5,000 grams per mole, or from about 600 grams per mole to about 5,000grams per mole. The number average molecular weight of the polyetherblock can range from about 100 to about 6,000, from about 400 to about3000, or from about 200 to about 3,000. The polyether (PE) content (x)of the poly(ether block amide) polymer can be from about 0.05 to about0.8 (i.e., from about 5 mole percent to about 80 mole percent). Thepolyether blocks can be present in the polyamide in an amount of fromabout 10 weight percent to about 50 weight percent, from about 20 weightpercent to about 40 weight percent, or from about 30 weight percent toabout 40 weight percent. The polyamide blocks can be present in thepolyamide in an amount of from about 50 weight percent to about 90weight percent, from about 60 weight percent to about 80 weight percent,or from about 70 weight percent to about 90 weight percent.

The polyether blocks can contain units other than ethylene oxide units,such as, for example, propylene oxide or polytetrahydrofuran (whichleads to polytetramethylene glycol sequences). It is also possible touse simultaneously PEG blocks, i.e., those consisting of ethylene oxideunits, polypropylene glycol (PPG) blocks, i.e. those consisting ofpropylene oxide units, and poly(tetramethylene ether)glycol (PTMG)blocks, i.e. those consisting of tetramethylene glycol units, also knownas polytetrahydrofuran. PPG or PTMG blocks are advantageously used. Theamount of polyether blocks in these copolymers containing polyamide andpolyether blocks can be from about 10 weight percent to about 50 weightpercent of the copolymer, or from about 35 weight percent to about 50weight percent.

The copolymers containing polyamide blocks and polyether blocks can beprepared by any means for attaching the polyamide blocks and thepolyether blocks. In practice, two processes are essentially used, onebeing a 2-step process and the other a one-step process.

In the two-step process, the polyamide blocks having dicarboxylic chainends are prepared first, and then, in a second step, these polyamideblocks are linked to the polyether blocks. The polyamide blocks havingdicarboxylic chain ends are derived from the condensation of polyamideprecursors in the presence of a chain-stopper dicarboxylic acid. If thepolyamide precursors are only lactams or α,ω-aminocarboxylic acids, adicarboxylic acid is added. If the precursors already comprise adicarboxylic acid, this is used in excess with respect to thestoichiometry of the diamines. The reaction usually takes place fromabout 180 to about 300 degrees C., such as from about 200 degrees toabout 290 degrees C., and the pressure in the reactor can be set fromabout 5 to about 30 bar and maintained for approximately 2 to 3 hours.The pressure in the reactor is slowly reduced to atmospheric pressureand then the excess water is distilled off, for example for one or twohours.

Once the polyamide having carboxylic acid end groups has been prepared,the polyether, the polyol and a catalyst are then added. The totalamount of polyether can be divided and added in one or more portions, ascan the catalyst. The polyether is added first and the reaction of theOH end groups of the polyether and of the polyol with the COOH endgroups of the polyamide starts, with the formation of ester linkages andthe elimination of water. Water is removed as much as possible from thereaction mixture by distillation and then the catalyst is introduced inorder to complete the linking of the polyamide blocks to the polyetherblocks. This second step takes place with stirring, preferably under avacuum of at least 50 millibar (5000 Pascals) at a temperature such thatthe reactants and the copolymers obtained are in the molten state. Byway of example, this temperature can be from about 100 to about 400degrees C., such as from about 200 to about 250 degrees C. The reactionis monitored by measuring the torque exerted by the polymer melt on thestirrer or by measuring the electric power consumed by the stirrer. Theend of the reaction is determined by the value of the torque or of thetarget power. The catalyst is defined as being any product whichpromotes the linking of the polyamide blocks to the polyether blocks byesterification. The catalyst can be a derivative of a metal (M) chosenfrom the group formed by titanium, zirconium and hafnium. The derivativecan be prepared from a tetraalkoxides consistent with the generalformula M(OR)₄, in which M represents titanium, zirconium or hafnium andR, which can be identical or different, represents linear or branchedalkyl radicals having from 1 to 24 carbon atoms.

The catalyst can comprise a salt of the metal (M), particularly the saltof (M) and of an organic acid and the complex salts of the oxide of (M)and/or the hydroxide of (M) and an organic acid. The organic acid can beformic acid, acetic acid, propionic acid, butyric acid, valeric acid,caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid,stearic acid, oleic acid, linoleic acid, linolenic acid,cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, salicylicacid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipicacid, maleic acid, fumaric acid, phthalic acid or crotonic acid. Theorganic acid can be an acetic acid or a propionic acid. M can bezirconium and such salts are called zirconyl salts, e.g., thecommercially available product sold under the name zirconyl acetate.

The weight proportion of catalyst can vary from about 0.01 to about 5percent of the weight of the mixture of the dicarboxylic polyamide withthe polyetherdiol and the polyol. The weight proportion of catalyst canvary from about 0.05 to about 2 percent of the weight of the mixture ofthe dicarboxylic polyamide with the polyetherdiol and the polyol.

In the one-step process, the polyamide precursors, the chain stopper andthe polyether are blended together; what is then obtained is a polymerhaving essentially polyether blocks and polyamide blocks of highlyvariable length, but also the various reactants that have reactedrandomly, which are distributed randomly along the polymer chain. Theyare the same reactants and the same catalyst as in the two-step processdescribed above. If the polyamide precursors are only lactams, it isadvantageous to add a little water. The copolymer has essentially thesame polyether blocks and the same polyamide blocks, but also a smallportion of the various reactants that have reacted randomly, which aredistributed randomly along the polymer chain. As in the first step ofthe two-step process described above, the reactor is closed and heated,with stirring. The pressure established is from about 5 to about 30 bar.When the pressure no longer changes, the reactor is put under reducedpressure while still maintaining vigorous stirring of the moltenreactants. The reaction is monitored as previously in the case of thetwo-step process.

The proper ratio of polyamide to polyether blocks can be found in asingle poly(ether block amide), or a blend of two or more differentcomposition poly(ether block amide)s can be used with the proper averagecomposition. It can be useful to blend a block copolymer having a highlevel of polyamide groups with a block copolymer having a higher levelof polyether blocks, to produce a blend having an average level ofpolyether blocks of about 20 to about 40 weight percent of the totalblend of poly(amid-block-ether) copolymers, or about 30 to about 35weight percent. The copolymer can comprise a blend of two differentpoly(ether-block-amide)s comprising at least one block copolymer havinga level of polyether blocks below 35 weight percent, and a secondpoly(ether-block-amide) having at least 45 weight percent of polyetherblocks.

Exemplary commercially available copolymers include, but are not limitedto, those available under the tradenames of “VESTAMID” (EvonikIndustries, Essen, Germany); “PLATAMID” (Arkema, Colombes, France),e.g., product code H2694; “PEBAX” (Arkema), e.g., product code “PEBAXMH1657” and “PEBAX MV1074”; “PEBAX RNEW” (Arkema); “GRILAMID”(EMS-Chemie AG, Domat-Ems, Switzerland), or also to other similarmaterials produced by various other suppliers.

The polyamide can be physically crosslinked through, e.g., nonpolar orpolar interactions between the polyamide groups of the polymers. Inexamples where the polyamide is a copolyamide, the copolyamide can bephysically crosslinked through interactions between the polyamidegroups, and optionally by interactions between the copolymer groups.When the co-polyamide is physically crosslinked through interactionsbetween the polyamide groups, the polyamide segments can form theportion of the polymer referred to as the hard segment, and copolymersegments can form the portion of the polymer referred to as the softsegment. For example, when the copolyamide is a poly(ether-block-amide),the polyamide segments form the hard segments of the polymer, andpolyether segments form the soft segments of the polymer. Therefore, insome examples, the polymer can include a physically crosslinkedpolymeric network having one or more polymer chains with amide linkages.

The polyamide segment of the co-polyamide can include polyamide-11 orpolyamide-12 and the polyether segment can be a segment selected fromthe group consisting of polyethylene oxide, polypropylene oxide, andpolytetramethylene oxide segments, and combinations thereof.

The polyamide can be partially or fully covalently crosslinked, aspreviously described herein. In some cases, the degree of crosslinkingpresent in the polyamide is such that, when it is thermally processed,e.g., in the form of a yarn or fiber to form the articles of the presentdisclosure, the partially covalently crosslinked thermoplastic polyamideretains sufficient thermoplastic character that the partially covalentlycrosslinked thermoplastic polyamide is melted during the processing andre-solidifies. In other cases, the crosslinked polyamide is a thermosetpolymer.

Polyesters

The polymers can comprise a polyester. The polyester can comprise athermoplastic polyester, or a thermoset polyester. Additionally, thepolyester can be an elastomeric polyester, including a thermoplasticpolyester or a thermoset elastomeric polyester. The polyester can beformed by reaction of one or more carboxylic acids, or its ester-formingderivatives, with one or more bivalent or multivalent aliphatic,alicyclic, aromatic or araliphatic alcohols or a bisphenol. Thepolyester can be a polyester homopolymer having repeating polyestersegments of the same chemical structure. Alternatively, the polyestercan comprise a number of polyester segments having different polyesterchemical structures (e.g., polyglycolic acid segments, polylactic acidsegments, polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, etc.). The polyester segments havingdifferent chemical structure can be arranged randomly, or can bearranged as repeating blocks.

Exemplary carboxylic acids that can be used to prepare a polyesterinclude, but are not limited to, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decanedicarboxylic acid, undecane dicarboxylic acid, terephthalic acid,isophthalic acid, alkyl-substituted or halogenated terephthalic acid,alkyl-substituted or halogenated isophthalic acid, nitro-terephthalicacid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl thioetherdicarboxylic acid, 4,4′-diphenyl sulfone-dicarboxylic acid,4,4′-diphenyl alkylenedicarboxylic acid, naphthalene-2,6-dicarboxylicacid, cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylicacid. Exemplary diols or phenols suitable for the preparation of thepolyester include, but are not limited to, ethylene glycol, diethyleneglycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol,1,10-decanediol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol,2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol,1,4-cyclohexane dimethanol, and bis-phenol A.

The polyester can be a polybutylene terephthalate (PBT), apolytrimethylene terephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), a liquid crystal polyester, or a blendor mixture of two or more of the foregoing.

The polyester can be a co-polyester (i.e., a co-polymer includingpolyester segments and non-polyester segments). The co-polyester can bean aliphatic co-polyester (i.e., a co-polyester in which both thepolyester segments and the non-polyester segments are aliphatic).Alternatively, the co-polyester can include aromatic segments. Thepolyester segments of the co-polyester can comprise or consistessentially of polyglycolic acid segments, polylactic acid segments,polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, or any combination thereof. The polyestersegments of the co-polyester can be arranged randomly, or can bearranged as repeating blocks.

For example, the polyester can be a block co-polyester having repeatingblocks of polymeric units of the same chemical structure which arerelatively harder (hard segments), and repeating blocks of the samechemical structure which are relatively softer (soft segments). In blockco-polyesters, including block co-polyesters having repeating hardsegments and soft segments, physical crosslinks can be present withinthe blocks or between the blocks or both within and between the blocks.The polymer can comprise or consist essentially of an elastomericco-polyester having repeating blocks of hard segments and repeatingblocks of soft segments.

The non-polyester segments of the co-polyester can comprise or consistessentially of polyether segments, polyamide segments, or both polyethersegments and polyamide segments. The co-polyester can be a blockco-polyester, or can be a random co-polyester. The co-polyester can beformed from the polycondensation of a polyester oligomer or prepolymerwith a second oligomer prepolymer to form a block copolyester.Optionally, the second prepolymer can be a hydrophilic prepolymer. Forexample, the co-polyester can be formed from the polycondensation ofterephthalic acid or naphthalene dicarboxylic acid with ethylene glycol,1,4-butanediol, or 1,3-propanediol. Examples of co-polyesters includepolyethylene adipate, polybutylene succinate,poly(3-hydroxbutyrate-co-3-hydroxyvalerate), polyethylene terephthalate,polybutylene terephthalate, polytrimethylene terephthalate, polyethylenenapthalate, and combinations thereof. The co-polyamide can comprise orconsist of polyethylene terephthalate.

The polyester can be a block copolymer comprising segments of one ormore of polybutylene terephthalate (PBT), a polytrimethyleneterephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), and a liquid crystal polyester. Forexample, a suitable polyester that is a block copolymer can be a PET/PEIcopolymer, a polybutylene terephthalate/tetraethylene glycol copolymer,a polyoxyalkylenediimide diacid/polybutylene terephthalate copolymer, ora blend or mixture of any of the foregoing.

The polyester can be a biodegradable resin, for example, a copolymerizedpolyester in which poly(α-hydroxy acid) such as polyglycolic acid orpolylactic acid is contained as principal repeating units.

The disclosed polyesters can be prepared by a variety ofpolycondensation methods known to the skilled artisan, such as a solventpolymerization or a melt polymerization process.

Polyolefins

The polymers can comprise or consist essentially of a polyolefin. Thepolyolefin can be a thermoplastic polyolefin or a thermoset polyolefin.Additionally, the polyolefin can be an elastomeric polyolefin, includinga thermoplastic elastomeric polyolefin or a thermoset elastomericpolyolefin. Exemplary polyolefins can include polyethylene,polypropylene, and olefin elastomers (e.g., metallocene-catalyzed blockcopolymers of ethylene and α-olefins having 4 to about 8 carbon atoms).The polyolefin can be a polymer comprising a polyethylene, anethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), apolybutene, a polyisobutylene, a poly-4-methylpent-1-ene, apolyisoprene, a polybutadiene, a ethylene-methacrylic acid copolymer,and an olefin elastomer such as a dynamically cross-linked polymerobtained from polypropylene (PP) and an ethylene-propylene rubber(EPDM), and blends or mixtures of the foregoing. Further exemplarypolyolefins include polymers of cycloolefins such as cyclopentene ornorbornene.

It is to be understood that polyethylene, which optionally can becrosslinked, is inclusive a variety of polyethylenes, including lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE), medium density polyethylene (MDPE), high densitypolyethylene (HDPE), high density and high molecular weight polyethylene(HDPE-HMW), high density and ultrahigh molecular weight polyethylene(HDPE-UHMW), and blends or mixtures of any the foregoing polyethylenes.A polyethylene can also be a polyethylene copolymer derived frommonomers of monolefins and diolefins copolymerized with a vinyl, acrylicacid, methacrylic acid, ethyl acrylate, vinyl alcohol, and/or vinylacetate. Polyolefin copolymers comprising vinyl acetate-derived unitscan be a high vinyl acetate content copolymer, e.g., greater than about50 weight percent vinyl acetate-derived composition.

The polyolefin can be formed through free radical, cationic, and/oranionic polymerization by methods well known to those skilled in the art(e.g., using a peroxide initiator, heat, and/or light). The disclosedpolyolefin can be prepared by radical polymerization under high pressureand at elevated temperature. Alternatively, the polyolefin can beprepared by catalytic polymerization using a catalyst that normallycontains one or more metals from group IVb, Vb, VIb or VIII metals. Thecatalyst usually has one or more than one ligand, typically oxides,halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/oraryls that can be either p- or s-coordinated complexed with the groupIVb, Vb, VIb or VIII metal. The metal complexes can be in the free formor fixed on substrates, typically on activated magnesium chloride,titanium(III) chloride, alumina or silicon oxide. The metal catalystscan be soluble or insoluble in the polymerization medium. The catalystscan be used by themselves in the polymerization or further activatorscan be used, typically a group Ia, IIa and/or IIIa metal alkyls, metalhydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes.The activators can be modified conveniently with further ester, ether,amine or silyl ether groups.

Suitable polyolefins can be prepared by polymerization of monomers ofmonolefins and diolefins as described herein. Exemplary monomers thatcan be used to prepare the polyolefin include, but are not limited to,ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene,3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixturesthereof.

Suitable ethylene-α-olefin copolymers can be obtained bycopolymerization of ethylene with an α-olefin such as propylene,butene-1, hexene-1, octene-1,4-methyl-1-pentene or the like havingcarbon numbers of 3 to 12.

Suitable dynamically cross-linked polymers can be obtained bycross-linking a rubber component as a soft segment while at the sametime physically dispersing a hard segment such as PP and a soft segmentsuch as EPDM by using a kneading machine such as a Banbury mixer and abiaxial extruder.

The polyolefin can be a mixture of polyolefins, such as a mixture of twoor more polyolefins disclosed herein above. For example, a suitablemixture of polyolefins can be a mixture of polypropylene withpolyisobutylene, polypropylene with polyethylene (for example PP/HDPE,PP/LDPE) or mixtures of different types of polyethylene (for exampleLDPE/HDPE).

The polyolefin can be a copolymer of suitable monolefin monomers or acopolymer of a suitable monolefin monomer and a vinyl monomer. Exemplarypolyolefin copolymers include ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

The polyolefin can be a polypropylene homopolymer, a polypropylenecopolymers, a polypropylene random copolymer, a polypropylene blockcopolymer, a polyethylene homopolymer, a polyethylene random copolymer,a polyethylene block copolymer, a low density polyethylene (LDPE), alinear low density polyethylene (LLDPE), a medium density polyethylene,a high density polyethylene (HDPE), or blends or mixtures of one or moreof the preceding polymers.

The polyolefin can be a polypropylene. The term “polypropylene,” as usedherein, is intended to encompass any polymeric composition comprisingpropylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as ethylene, butylene, and the like). Such a term also encompassesany different configuration and arrangement of the constituent monomers(such as atactic, syndiotactic, isotactic, and the like). Thus, the termas applied to fibers is intended to encompass actual long strands,tapes, threads, and the like, of drawn polymer. The polypropylene can beof any standard melt flow (by testing); however, standard fiber gradepolypropylene resins possess ranges of Melt Flow Indices between about 1and 1000.

The polyolefin can be a polyethylene. The term “polyethylene,” as usedherein, is intended to encompass any polymeric composition comprisingethylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as propylene, butylene, and the like). Such a term alsoencompasses any different configuration and arrangement of theconstituent monomers (such as atactic, syndiotactic, isotactic, and thelike). Thus, the term as applied to fibers is intended to encompassactual long strands, tapes, threads, and the like, of drawn polymer. Thepolyethylene can be of any standard melt flow (by testing); however,standard fiber grade polyethylene resins possess ranges of Melt FlowIndices between about 1 and 1000.

The thermoplastic and/or thermosetting material can further comprise oneor more processing aids. The processing aid can be a non-polymericmaterial. These processing aids can be independently selected from thegroup including, but not limited to, curing agents, initiators,plasticizers, mold release agents, lubricants, antioxidants, flameretardants, dyes, pigments, reinforcing and non-reinforcing fillers,fiber reinforcements, and light stabilizers.

Now having described various aspects of the present disclosure,additional discussion is provided regarding the structure of thebladder. The bladder can be unfilled, partially inflated, or fullyinflated when the structural design (e.g., multi-layer optical film) isdisposed onto the bladder. The bladder is a bladder capable of includinga volume of a fluid. An unfilled bladder is a fluid-fillable bladder anda filled bladder that has been at least partially inflated with a fluidat a pressure equal to or greater than atmospheric pressure. Whendisposed onto or incorporated into an article of footwear, apparel, orsports equipment, the bladder is generally, at that point, afluid-filled bladder. The fluid be a gas or a liquid. The gas caninclude air, nitrogen gas (N₂), or other appropriate gas.

The bladder can have a gas transmission rate for nitrogen gas, forexample, where a bladder wall of a given thickness has a gastransmission rate for nitrogen that is at least about ten times lowerthan the gas transmission rate for nitrogen of a butyl rubber layer ofsubstantially the same thickness as the thickness of the bladderdescribed herein. The bladder can have a first bladder wall having afirst bladder wall thickness (e.g., about 0.1 to 40 mils). The bladdercan have a first bladder wall that can have a gas transmission rate(GTR) for nitrogen gas of less than about 15 cm³/m²·atm·day, less thanabout 10 m³/m²·atm·day, less than about 5 cm³/m²·atm·day, less thanabout 1 cm³/m²·atm·day (e.g., from about 0.001 cm³/m²·atm·day to about 1cm³/m²·atm·day, about 0.01 cm³/m²·atm·day to about 1 cm³/m²·atm·day orabout 0.1 cm³/m²·atm·day to about 1 cm³/m²·atm·day) for an average wallthickness of 20 mils. The bladder can have a first bladder wall having afirst bladder wall thickness, where the first bladder wall has a gastransmission rate of 15 cm³/m²·atm·day or less for nitrogen for anaverage wall thickness of 20 mils.

In an aspect, the bladder has a bladder wall having an interior-facingside and an exterior-facing side, where the interior-facing side definesat least a portion of an interior region of the bladder. The multi-layeroptical film having a first side and a second opposing side can bedisposed on the exterior-facing side of the bladder, the interior-facingside of the bladder, or both. The exterior-facing side of the bladder,the interior-facing side of the bladder, or both can include a pluralityof topographical structures extending from the exterior-facing side ofthe bladder wall, the interior-facing side of the bladder, or both,where the first side or the second side of the multi-layer optical filmis disposed on the exterior-facing side of the bladder wall and coveringsome or all of the plurality of topographical structures, theinterior-facing side of the bladder wall and covering some or all of theplurality of topographical structures, or both, and wherein themulti-layer optical film imparts a structural color to the bladder wall.The primer layer can be disposed on the exterior-facing side of thebladder, the interior-facing side of the bladder, or both, between thebladder wall and the multi-layer optical film.

In a particular aspect, the bladder can include a top wall operablysecured to the footwear upper, a bottom wall opposite the top wall, andone or more sidewalls extending between the top wall and the bottom wallof the inflated bladder. The top wall, the bottom wall, and the one ormore sidewalls collectively define an interior region of the inflatedbladder, and wherein the one or more sidewalls each comprise anexterior-facing side. The multi-layer optical film having a first sideand a second opposing side can be disposed on the exterior-facing sideof the bladder, the interior-facing side of the bladder, or both. Theexterior-facing side of the bladder, the interior-facing side of thebladder, or both can include a plurality of topographical structuresextending from the exterior-facing side of the bladder wall, theinterior-facing side of the bladder, or both, where the first side orthe second side of the multi-layer optical film is disposed on theexterior-facing side of the bladder wall and covering some or all of theplurality of topographical structures, the interior-facing side of thebladder wall and covering some or all of the plurality of topographicalstructures, or both, and wherein the multi-layer optical film imparts astructural color to the bladder wall. The primer layer can be disposedon the exterior-facing side of the bladder, the interior-facing side ofthe bladder, or both, between the bladder wall and the multi-layeroptical film.

An accepted method for measuring the relative permeance, permeability,and diffusion of inflated bladders is ASTM D-1434-82-V. See, e.g., U.S.Pat. No. 6,127,026, which is incorporated by reference as if fully setforth herein. According to ASTM D-1434-82-V, permeance, permeability anddiffusion are measured by the following formulae:

Permeance(quantity of gas)/[(area)×(time)×(pressure difference)]=permeance(GTR)/(pressure difference)=cm³/m²·atm·day (i.e., 24 hours)Permeability[(quantity of gas)×(film thickness)][(area)×(time)×(pressuredifference)]=permeability [(GTR)×(film thickness)]/(pressuredifference)=[(cm³)(mil)]/m²·atm·day (i.e., 24 hours)Diffusion at One Atmosphere(quantity of gas)/[(area)×(time)]=GTR=cm³/m²·day (i.e., 24 hours)

The bladder can include a bladder wall that includes a film including atleast one polymeric layer or at least two or more polymeric layers. Eachof the polymeric layers can be about 0.1 to 40 mils in thickness.

The polymeric layer can be formed of polymer material such as athermoplastic material as described above and herein. The thermoplasticmaterial can include an elastomeric material, such as a thermoplasticelastomeric material. The thermoplastic materials can includethermoplastic polyurethane (TPU), such as those described above andherein. The thermoplastic materials can include polyester-based TPU,polyether-based TPU, polycaprolactone-based TPU, polycarbonate-basedTPU, polysiloxane-based TPU, or combinations thereof. Non-limitingexamples of thermoplastic material that can be used include:“PELLETHANE” 2355-85ATP and 2355-95AE (Dow Chemical Company of Midland,Mich., USA), “ELASTOLLAN” (BASF Corporation, Wyandotte, Mich., USA) and“ESTANE” (Lubrizol, Brecksville, Ohio, USA), all of which are eitherester or ether based. Additional thermoplastic material can includethose described in U.S. Pat. Nos. 5,713,141; 5,952,065; 6,082,025;6,127,026; 6,013,340; 6,203,868; and 6,321,465, which are incorporatedherein by reference.

The polymeric layer can be formed of one or more of the following:ethylene-vinyl alcohol copolymers (EVOH), poly(vinyl chloride),polyvinylidene polymers and copolymers (e.g., polyvinylidene chloride),polyamides (e.g., amorphous polyamides), acrylonitrile polymers (e.g.,acrylonitrile-methyl acrylate copolymers), polyurethane engineeringplastics, polymethylpentene resins, ethylene-carbon monoxide copolymers,liquid crystal polymers, polyethylene terephthalate, polyether imides,polyacrylic imides, and other polymeric materials known to haverelatively low gas transmission rates. Blends and alloys of thesematerials as well as with the TPUs described herein and optionallyincluding combinations of polyimides and crystalline polymers, are alsosuitable. For instance, blends of polyimides and liquid crystalpolymers, blends of polyamides and polyethylene terephthalate, andblends of polyamides with styrenics are suitable.

Specific examples of polymeric materials of the polymeric layer caninclude acrylonitrile copolymers such as “BAREX” resins, available fromIneos (Rolle, Switzerland); polyurethane engineering plastics such as“ISPLAST” ETPU available from Lubrizol (Brecksville, Ohio, USA);ethylene-vinyl alcohol copolymers marketed under the tradenames “EVAL”by Kuraray (Houston, Tex., USA), “SOARNOL” by Nippon Gohsei (Hull,England), and “SELAR OH” by DuPont (Wilmington, Del., USA);polyvinylidiene chloride available from S.C. Johnson (Racine, Wis., USA)under the tradename “SARAN”, and from Solvay (Brussels, Belgium) underthe tradename “IXAN”; liquid crystal polymers such as “VECTRA” fromCelanese (Irving, Tex., USA) and “XYDAR” from Solvay; “MDX6” nylon, andamorphous nylons such as “NOVAMID” X21 from Koninklijke DSM N.V(Heerlen, Netherlands), “SELAR PA” from DuPont; polyetherimides soldunder the tradename “ULTEM” by SABIC (Riyadh, Saudi Arabia); poly(vinylalcohol)s; and polymethylpentene resins available from Mitsui Chemicals(Tokyo, Japan) under the tradename “TPX”.

Each polymeric layer of the film can be formed of a thermoplasticmaterial which can include a combination of thermoplastic polymers. Inaddition to one or more thermoplastic polymers, the thermoplasticmaterial can optionally include a colorant, a filler, a processing aid,a free radical scavenger, an ultraviolet light absorber, and the like.Each polymeric layer of the film can be made of a different ofthermoplastic material including a different type of thermoplasticpolymer.

The bladder can be made by applying heat, pressure and/or vacuum to afilm. The bladder (e.g., one or more polymeric layers) can be formedusing one or more polymeric materials, and forming the bladder using oneor more processing techniques including, for example, extrusion, blowmolding, injection molding, vacuum molding, rotary molding, transfermolding, pressure forming, heat sealing, casting, low-pressure casting,spin casting, reaction injection molding, radio frequency (RF) welding,and the like. The bladder can be made by co-extrusion followed by heatsealing or welding to give an inflatable bladder, which can optionallyinclude one or more valves (e.g., one way valves) that allows thebladder to be filled with the fluid (e.g., gas).

As described herein, the multi-layer optical film can be disposed ontothe interior-facing surface (side) of the bladder or the exterior-facingsurface (side) of the bladder. The textured layer can be theinterior-facing surface (side) or the exterior-facing surface (side) ofthe bladder. The multi-layer optical film can include the optical layerand optionally the primer layer and texture structure. The texturedlayer can be the interior-facing surface (side) or the exterior-facingsurface (side) of the bladder (e.g., where the interior-facing orexterior-facing side is made of a thermoplastic material) and the primerlayer disposed thereon and the multi-layer optical film disposed on theprimer layer.

Now having described embodiments of the disclosure, evaluation ofvarious properties and characteristics described herein are by varioustesting procedures as described herein below.

Method to Determine the Melting Temperature, and Glass TransitionTemperature. The melting temperature and glass transition temperatureare determined using a commercially available Differential Scanningcalorimeter (“DSC”) in accordance with ASTM D3418-97. Briefly, a 10-15gram sample is placed into an aluminum DSC pan and then the lead wassealed with the crimper press. The DSC is configured to scan from −100degrees C. to 225 degrees C. with a 20 degrees C./minute heating rate,hold at 225 degrees C. for 2 minutes, and then cool down to 25 degreesC. at a rate of −10 degrees C./minute. The DSC curve created from thisscan is then analyzed using standard techniques to determine the glasstransition temperature and the melting temperature.

Method to Determine the Melt Flow Index. The melt flow index isdetermined according to the test method detailed in ASTM D1238-13Standard Test Method for Melt Flow Rates of Thermoplastics by ExtrusionPlastometer, using Procedure A described therein. Briefly, the melt flowindex measures the rate of extrusion of thermoplastics through anorifice at a prescribed temperature and load. In the test method,approximately 7 grams of the material is loaded into the barrel of themelt flow apparatus, which has been heated to a temperature specifiedfor the material. A weight specified for the material is applied to aplunger and the molten material is forced through the die. A timedextrudate is collected and weighed. Melt flow rate values are calculatedin grams/10 min.

Various embodiments of the present disclosure are described below ineach of the sets of clauses. For each of the clauses, “disposing” can bereplaced with “operably disposing”.

Clause 1. An article comprising:

a bladder having a first bladder wall, the first bladder wall having afirst bladder wall thickness, an exterior-facing side comprising a firstthermoplastic material, and an interior-facing side comprising a secondthermoplastic material, wherein the first bladder wall has a gastransmission rate of 15 cm³/m²·atm·day or less for nitrogen for anaverage wall thickness of 20 mils; and

an multi-layer optical film disposed on or within the bladder, whereinthe multi-layer optical film has a first side and a second side, whereinthe first side and the second side are on opposing sides, wherein thefirst side or the second side of the multi-layer optical film isdisposed on the exterior-facing side of the first bladder wall, on theinterior-facing side of the first bladder wall, or on a side of acomponent in an internal cavity of the bladder, and wherein the firstside of the multi-layer optical film, the second side of the multi-layeroptical film, or both impart a structural color to the bladder.

Clause 2. The article of clause 1, wherein the exterior-facing side orthe interior-facing side of the first bladder wall, or the first side orthe second side of the multi-layer optical film, or any combinationthereof, comprise a textured surface, and a combination of the texturedsurface and the multi-layer optical film impart the structural color.Clause 3. The article of any of the preceding clauses, wherein thetextured surface is part of a textured layer or textured structure.Clause 4. The article of any of the preceding clauses, wherein themulti-layer optical film comprises the textured surface.Clause 5. The article of any of the preceding clauses, wherein thetextured surface, the textured layer or the textured structure is on thefirst side of the multi-layer optical film, and wherein the first sideof the multi-layer optical film is disposed onto the exterior-facingsurface of the first bladder wall.Clause 6. The article of any of the preceding clauses, wherein thetextured surface, the textured layer or the textured structure is on thesecond side of the multi-layer optical film, wherein the first side ofthe multi-layer optical film is disposed onto the interior-facingsurface of the first bladder wall.Clause 7. The article of any of the preceding clauses, wherein thetextured surface has a plurality of topographical structures andplurality of flat areas.Clause 8. The article of any of the preceding clauses, wherein thetextured surface includes a plurality of topographical structures andflat planar areas, and wherein the topographical structures extend abovethe flat areas of the textured surface.Clause 9. The article of any of the preceding clauses, wherein thedimensions of the topographical structures, a shape of the topographicalstructures, a spacing among the plurality of the topographicalstructures, in combination with the optical layer impart the structuralcolor.Clause 10. The article of any of the preceding clauses, wherein, over anarea of the textured surface having a surface area of at least 5 squaremillimeters, the topographical structures are in random positionsrelative to one another.Clause 11. The article of any of the preceding clauses, wherein spacingamong the topographical structures is set to reduce distortion effectsof the topographical structures from interfering with one another in theimparted structural color.Clause 12. The article of any of the preceding clauses, wherein thetopographical structures and the flat areas result in at least oneoptical layer of the multi-layer optical film having an undulatingtopography, wherein there is a planar region between neighboringdepressions, elevations, or both that is planar with the flat planarareas of the textured surface, wherein the planar region has dimensionsrelative to the topographical structures to impart the structural color.Clause 13. The article of any of the preceding clauses, wherein thetopographical structures and the flat areas cause at least one layer ofthe multi-layer optical film to have an undulating topography across thetextured structure.Clause 14. The article of any of the preceding clauses, wherein thetopographical structures and the flat areas cause each layer of themulti-layer optical film to have an undulating topography across thetextured structure.Clause 15. The article of any of the preceding clauses, wherein themulti-layer optical film includes at least two optical layers.Clause 16. The article of any preceding article clause, wherein at leastone of the layers of the multi-layer optical film comprises or consistsessentially of a metal, wherein optionally the metal is selected fromtitanium or silicon.Clause 17. The article of any preceding article clause, wherein themulti-layer optical film comprises at least one layer comprising orconsisting essentially of a metal oxide, wherein optionally the metaloxide is titanium dioxide or silicon dioxide.Clause 18. The article of any preceding article claim, wherein themulti-layer optical film comprises at least three layers, including afirst layer comprising a metal, and a second layer comprising a metaloxide.Clause 19. The article of any of the preceding clauses, wherein themulti-layer optical film comprises a multilayer reflector or amultilayer filter.Clause 20. The article of any of the preceding clauses, wherein themultilayer reflector has at least two layers, including at least twoadjacent layers having different refractive indices.Clause 21. The article of any of the preceding clauses, wherein therefractive indices of the at least two adjacent layers differ by atleast 5 percent, optionally at least 10 percent, or optionally at least15 percent.Clause 22. The article of any of the preceding clauses, wherein at leastone of the layers of the multilayer reflector has a thickness that isabout one fourth of the wavelength of visible light to be reflected bythe multi-layer optical film to impart the structural color.Clause 23. The article of any of the preceding clauses, wherein at leastone of the layers of the multilayer reflector comprises a materialselected from the group consisting of: silicon dioxide, titaniumdioxide, zinc sulfide, magnesium fluoride, tantalum pentoxide, and acombination thereof.Clause 24. The article of any preceding clause, wherein the structuralcolor of the bladder is visible to a viewer having 20/20 visual acuityand normal color vision from a distance of about 1 meter from thebladder.Clause 25. The article of any preceding clause, wherein the structuralcolor imparted to the bladder has a single hue across theexterior-facing side of the bladder, regardless of viewing angle.Clause 26. The article of any preceding clause, wherein the structuralcolor imparted to the bladder includes two or more hues, each of the twoor more hues being localized to a single region across theexterior-facing side of the bladder, and wherein the two or more hues donot shift as viewing angle is varied.Clause 27. The article of any preceding clause, wherein the structuralcolor imparted to the bladder is iridescent.Clause 28. The article of any preceding clause, wherein the structuralcolor of the bladder has limited iridescence.Clause 29. The article of the preceding clause, wherein the structuralcolor has limited iridescence such that, when each color visible at eachpossible angle of observation is assigned to a single hue selected fromthe group consisting of the primary, secondary and tertiary colors onthe red yellow blue (RYB) color wheel, all of the assigned hues fallinto a single hue group, wherein the single hue group is one of a)green-yellow, yellow, and yellow-orange; b) yellow, yellow-orange andorange; c) yellow-orange, orange, and orange-red; d) orange-red, andred-purple; e) red, red-purple, and purple; f) red-purple, purple, andpurple-blue; g) purple, purple-blue, and blue; h) purple-blue, blue, andblue-green; i) blue, blue-green and green; and j) blue-green, green, andgreen-yellow.Clause 30. The article of any of the preceding clauses, wherein themulti-layer optical film, as disposed onto the bladder, when measuredaccording to the CIE 1976 color space under a given illuminationcondition at three observation angles between −15 degrees and +60degrees, has a first color measurement at a first angle of observationhaving coordinates L₁* and a₁* and b_(1*), and a second colormeasurement at a second angle of observation having coordinates L₂* anda₂* and b₂*, and a third color measurement at a third angle ofobservation having coordinates L₃* and a₃* and b₃*, wherein the L_(1*),L_(2*), and L₃* values may be the same or different, wherein the a₁*,a₂*, and a₃* coordinate values may be the same or different, wherein theb_(1*), b₂*, and b₃* coordinate values may be the same or different, andwherein the range of the combined a₁*, a₂* and a₃* values is less thanabout 40% of the overall scale of possible a* values, optionally is lessthan about 30% of the overall scale of possible a* values, optionally isless than about 20% of the overall scale of possible a* values, or isless than about 10% of the overall scale of possible a* values.Clause 31. The article of any of the preceding clauses, wherein themulti-layer optical film, as disposed onto the bladder, when measuredaccording to the CIE 1976 color space under a given illuminationcondition at three observation angles between −15 degrees and +60degrees, has a first color measurement at a first angle of observationhaving coordinates L₁* and a₁* and b_(1*), and a second colormeasurement at a second angle of observation having coordinates L₂* anda₂* and b₂*, and a third color measurement at a third angle ofobservation having coordinates L₃* and a₃* and b₃*, wherein the L_(1*),L_(2*), and L₃* values may be the same or different, wherein the a₁*,a₂*, and a₃* coordinate values may be the same or different, wherein theb_(1*), b₂*, and b₃* coordinate values may be the same or different, andwherein the range of the combined b_(1*), b₂* and b₃* values is lessthan about 40% of the overall scale of possible b* values, optionally isless than about 30% of the overall scale of possible b* values,optionally is less than about 20% of the overall scale of possible b*values, or optionally is less than about 10% of the overall scale ofpossible b* values.Clause 32. The article of any of the preceding clauses, wherein themulti-layer optical film, as disposed onto the bladder, when measuredaccording to the CIE 1976 color space under a given illuminationcondition at two observation angles between −15 degrees and +60 degrees,has a first color measurement at a first angle of observation havingcoordinates L₁* and a₁* and b_(1*), and a second color measurement at asecond angle of observation having coordinates L₂* and a₂* and b₂*,wherein the L₁* and L₂* values may be the same or different, wherein thea₁* and a₂* coordinate values may be the same or different, wherein theb₁* and b₂* coordinate values may be the same or different, and whereinthe ΔE*_(ab) between the first color measurement and the second colormeasurement is less than or equal to about 100, whereΔE*_(ab)=[(L₁*−L₂)²+(a₁*−a₂*)₂+(b₁*−b₂*)²]^(1/2) optionally is less thanor equal to about 80, or optionally is less than or equal to about 60.Clause 33. The article of any of the preceding clauses, wherein themulti-layer optical film, as disposed onto the bladder, when measuredaccording to the CIELCH color space under a given illumination conditionat three observation angles between −15 degrees and +60 degrees, has afirst color measurement at a first angle of observation havingcoordinates L₁* and C₁* and h₁°, and a second color measurement at asecond angle of observation having coordinates L₂* and C₂* and h₂°, anda third color measurement at a third angle of observation havingcoordinates L₃* and C₃* and h₃°, wherein the L₁*, L₂*, and L₃* valuesmay be the same or different, wherein the C₁*, C₂*, and C₃* coordinatevalues may be the same or different, wherein the h₁°, h₂° and h₃°coordinate values may be the same or different, and wherein the range ofthe combined h₁°, h₂° and h₃° values is less than about 60 degrees,optionally is less than about 50 degrees, optionally is less than about40 degrees, optionally is less than about 30 degrees, or optionally isless than about 20 degrees.Clause 34. The article of any of the preceding clauses, wherein a primerlayer is disposed on the textured surface.Clause 35. The article of any of the preceding clauses, wherein theprimer layer is on the exterior-facing side of the bladder wall or onthe interior-facing side of the bladder wall, and the multi-layeroptical film is disposed on the primer layer.Clause 36. The article of any of the preceding clauses, wherein themulti-layer optical film is disposed on the first thermoplastic materialof the exterior-facing side or the second thermoplastic material of theinterior-facing side of the bladder wall, with the primer layer, thetextured surface, or both, positioned between the multi-layer opticalfilm and the first thermoplastic material.Clause 37. The article of any of the preceding clauses, wherein theprimer layer comprises a textured surface, and the textured surface ofthe primer layer, the primer layer, and the multi-layer optical filmimpart the structural color.Clause 38. The article of any of the preceding clauses, wherein theprimer layer is a digitally printed layer, an offset printed layer, apad printed layer, a screen printed layer, a flexographically printedlayer, or a heat transfer printed layer.Clause 39. The article of any of the preceding clauses, wherein theprimer layer comprises a paint.Clause 40. The article of any of the preceding clauses, wherein theprimer layer comprises an ink.Clause 41. The article of any of the preceding clauses, wherein theprimer layer comprises a reground, and at least partially degradedpolymer.Clause 42. The article of any of the preceding clauses, wherein theprimer layer is an oxide layer.Clause 43. The article of any of the preceding clauses, wherein theprimer layer comprises a metal oxide or a metal oxynitride.Clause 44. The article of any of the preceding clauses, wherein themetal oxide or metal oxynitride is doped.Clause 45. The article of any preceding clause, wherein the primer layerconsists essentially of a metal oxide, and optionally consistsessentially of titanium dioxide.Clause 46. The article of any preceding clause, wherein the primer layerconsists essentially of a doped metal oxide or a doped metal oxynitrideor both.Clause 47. The article of any preceding clause, wherein the primer layerhas a thickness of about 1 to about 200 micrometers, or optionally ofabout 10 to about 100 micrometers, or optionally of about 10 to about 80micrometers.Clause 48. The article of any of the preceding clauses, wherein theprimer layer is a coating, wherein the coating is a crosslinked coatingincluding a matrix of crosslinked polymers.Clause 49. The article of any of the preceding clauses, wherein thecoating comprises a plurality of solid pigment particles entrapped inthe matrix of crosslinked polymers.Clause 50. The article of any of the preceding clauses, wherein thematrix of crosslinked polymers includes crosslinked elastomericpolymers.Clause 51. The article of any of the preceding clauses, wherein thecrosslinked elastomeric polymers include crosslinked polyurethanehomopolymers or copolymers or both.Clause 52. The article of any of the preceding clauses, wherein thecrosslinked polyurethane copolymers include crosslinked polyesterpolyurethanes.Clause 53. The article of any of the preceding clauses, wherein, whenthe solid pigment particles are present, the solid pigment particles areselected from the group consisting of: metal and metal oxide pigments,carbon pigments, clay earth pigments, ultramarine pigments and acombination thereof.Clause 54. The article of any of the preceding clauses, wherein thecoating further comprises a dye.Clause 55. The article of any of the preceding clauses, wherein, whenthe dye is present, the dye is an acid dye.Clause 56. The article of any of the preceding clauses, wherein thecoating further comprises a quaternary ammonium compound.Clause 57. The article of any of the preceding clauses, wherein thequaternary ammonium compound is a tetrabutyl ammonium compound.Clause 58. The article of any of the preceding clauses, wherein thetetrabutyl ammonium compound is a tetrabutyl ammonium halide.Clause 59. The article of any of the preceding clauses, wherein thepolymeric coating composition, when present, comprises from 1 to 15weight percent of the quaternary ammonium compound.Clause 60. The article of any of the preceding clauses, wherein a molarratio of the acid dye to the quaternary ammonium compound ranges from3:1 to 1:3 Clause 61. The article of any of the preceding clauses,wherein the molar ratio of the acid dye to the quaternary ammoniumcompound ranges from 1.5:1 to 1:1.5.Clause 62. The article of any of the preceding clauses, wherein thematrix of crosslinked polymers of the coating include polyurethanepolymers.Clause 63. The article of any of the preceding clauses, wherein thepolyurethane polymers include thermoplastic polyurethane polymers.Clause 64. The article of any of the preceding clauses, wherein thepolyurethane polymers include elastomeric polyurethane polymers.Clause 65. The article of any of the preceding clauses, wherein thepolyurethane polymers include polyester polyurethane copolymers.Clause 66. The article of any of the preceding clauses, wherein thepolyurethane polymers consist essentially of polyester polyurethanecopolymers.Clause 67. The article of any of the preceding clauses, wherein theprimer layer has a thickness of about 3 to 200 nanometers.Clause 68. The article of any of the preceding clauses, wherein theprimer layer has a color selected from the group consisting of: black,dark brown, dark red, dark orange, dark yellow, dark green, dark cyan,dark blue, dark violet, grey, dark magenta, dark indigo, tones thereof,tints thereof, shades thereof, and a combination thereof.Clause 69. The article of any of the preceding clauses, wherein thecolor of the primer layer is different than the color of the structuralcolor.Clause 70. The article of any of the preceding clauses, wherein thecolor of the primer layer is different than the color of the structuralcolor under the criteria of any preceding clause.Clause 71. The article of any of the preceding clauses, wherein thefirst polymeric material, the second polymer material, both are athermoplastic material.Clause 72. The article of any of the preceding clauses, wherein thethermoplastic material is an elastomeric thermoplastic material.Clause 73. The article of any of the preceding clauses, wherein thethermoplastic material includes one or more thermoplastic polyurethanes.Clause 74. The article of any of the preceding clauses, wherein thethermoplastic material includes one or more thermoplastic polyurethanes,polyesters, polyamides, polyolefins, or a combination thereof.Clause 75. The article of any of the preceding clauses, wherein theelastomeric thermoplastic material includes a polyester polyurethanecopolymer.Clause 76. The article of any of the preceding clauses, wherein thefirst thermoplastic material and the second thermoplastic materialcomprise thermoplastic polymers of the same polymer type.Clause 77. The article of any of the preceding clauses, wherein thefirst thermoplastic material and the second thermoplastic materialcomprise thermoplastic polymers of different types.Clause 78. The article of any of the preceding clauses, wherein thefirst thermoplastic material comprises thermoplastic polyurethanes,optionally elastomeric thermoplastic polyurethanes, or optionallyelastomeric thermoplastic polyester polyurethane copolymers. Clause 79.The article of any of the preceding clauses, wherein the firstthermoplastic material comprises thermoplastic polyester polyurethanecopolymers.Clause 80. The article of any preceding article clause, wherein thefirst bladder wall includes a barrier membrane including layers of thefirst thermoplastic material alternating with layers of a thirdthermoplastic material.Clause 81. The article of any preceding article clause, wherein thethird thermoplastic material includes ethylene vinyl alcohol copolymers.Clause 82. The article of any of the preceding clauses, wherein thefirst side of the multi-layer optical film is disposed on theinterior-facing side of the first bladder wall, wherein the primer layeris disposed on the second side of the multi-layer optical film.Clause 83. The article of any of the preceding clauses, wherein themulti-layer optical film is disposed on the exterior-facing side of thefirst bladder wall, with the primer layer, the textured structure, orboth, positioned between the multi-layer optical film and theexterior-facing side of the first bladder wall.Clause 84. The article of any of the preceding clauses, wherein thebladder includes a component that includes the multi-layer optical filmof any of the clauses, optionally a texture surface of any of theclauses, and optionally a primer of any of the clauses in the internalcavity of the bladder.Clause 85. The article of any of the preceding clauses, wherein thecomponent is selected from a spacer formed of a solid polymericmaterial, a spacer formed of a foamed polymeric material, a spacerformed of a textile, or a combination thereof.Clause 86. An article of apparel, comprising a bladder, wherein thebladder is a bladder of any preceding article clause.Clause 87. An article of sporting equipment comprising a bladder,wherein the bladder is a bladder of any preceding article clause.Clause 88. An article of footwear, comprising a bladder, wherein thebladder is a bladder of any preceding article clause.Clause 89. An article of footwear, comprising a sole, wherein the soleincludes a bladder of any preceding article clause.Clause 90. A method of making an article of footwear, apparel orsporting equipment comprising:

affixing a bladder of any preceding article clause to a second element,forming an article of footwear, apparel or sporting equipment.

Clause 91. The method of any of the preceding clauses, wherein thearticle is an article of footwear comprising the bladder in a sole,further comprising affixing the sole to an upper to form the article offootwear.

Clause 92. The method of any of the preceding clauses, wherein themethod further comprises the step(s) of any of the following methodclauses.

Clause 93. A method of making a bladder, comprising:

disposing an multi-layer optical film onto an exterior-facing side or aninterior-facing side of a first bladder wall of a bladder, the bladderwall having a first bladder wall thickness and a gas transmission rateof 15 cm³/m²·atm·day or less for nitrogen for an average wall thicknessof 20 mils, wherein the exterior-facing side comprises a firstthermoplastic material and the interior-facing side comprises a secondthermoplastic material, wherein the first bladder wall has; wherein themulti-layer optical film has a first side and a second side, wherein thefirst side and the second side are on opposing sides, wherein the firstside or the second side of the multi-layer optical film is disposed onthe external-facing side of the bladder wall, or the interior-facingside of the first bladder wall, or on a component in an internal cavityof the bladder; and wherein the first side of the multi-layer opticalfilm, the second side of the multi-layer optical film, or both impart astructural color to the bladder.

Clause 94. The method of any of the preceding clauses, wherein themethod further comprises forming the bladder by applying heat, pressure,vacuum, or a combination thereof to a film, forming the bladder, whereinthe film has a gas transmission rate of 15 cm³/m²·atm·day or less fornitrogen for an average film thickness of 20 mils;

wherein the step of forming the bladder is conducted prior to orfollowing the disposing the multi-layer optical film onto theexterior-facing side or the internal-facing side of the bladder wall.

Clause 95. The method of any of the preceding clauses, wherein themethod further comprises inflating the bladder after the forming thebladder.

Clause 96. The method of any of the preceding clauses, wherein thedisposing the multi-layer optical film is conducted prior to inflatingthe bladder.

Clause 97. The method of any of the preceding clauses, wherein thedisposing the multi-layer optical film is conducted on an inflatedbladder.

Clause 98. The method of any of the preceding clauses, wherein atemperature of the inflated bladder is maintained at a temperature belowa glass transition temperature of the first thermoplastic materialduring the disposing.

Clause 99. The method of any of the preceding clauses, wherein atemperature of the inflated bladder is maintained at a temperature at orbelow 80 degrees C. during the disposing.

Clause 100. The method of any of the preceding clauses, wherein thedisposing includes disposing the first side of the multi-layer opticalfilm onto the exterior-facing side of the first bladder wall.

Clause 101. The method of any of the preceding clauses, wherein themethod further comprises forming a textured surface, a primer layer, orboth, on the exterior-facing side of the first bladder wall, or on theinterior-facing side of the first bladder wall, prior to the disposing.Clause 102. The method of any of the preceding clauses, wherein themulti-layer optical film includes a textured surface, a primer layer, orboth.Clause 103. The method of any of the preceding clauses, wherein thedisposing includes disposing the first side of the multi-layer opticalfilm onto the interior-facing side of the first bladder wall.Clause 104. The method of any of the preceding clauses, wherein theinterior-facing side of the first bladder wall includes a texturedsurface.Clause 105. The method of any of the preceding clauses, wherein thetextured surface is part of a textured layer or a textured structure.Clause 106. The method of any of the preceding clauses, wherein themulti-layer optical film includes the textured layer or texturedstructure.Clause 107. The method of any of the preceding clauses, wherein thetextured surface is a textured surface according to any precedingarticle clause.Clause 108. The method of any of the preceding clauses, wherein themulti-layer optical film is a multi-layer optical film according to anypreceding article clause.Clause 109. The method of any of the preceding clauses, furthercomprising disposing a primer layer on the exterior-facing side of thefirst bladder wall or on the interior-facing side of the first bladderwall prior to the disposing the multi-layer optical film; and, theprimer layer and the optical layer impart the structural color.Clause 110. The method of any of the preceding clauses, wherein theexterior-facing side or the interior-facing side includes a texturedsurface; the method further comprises forming a primer layer on thetextured surface prior to the disposing the multi-layer optical film;interior-facingexterior-facinginterior-facingexterior-facingand thetextured surface, the primer layer, and the optical layer impart thestructural color.Clause 111. The method of any of the preceding clauses, wherein formingthe primer layer comprises forming the primer layer using digitalprinting, offset printing, pad printing, screen printing, flexographicprinting, or heat transfer printing.Clause 112. The method of any of the preceding clauses, wherein thedisposing includes disposing the multi-layer optical film on acomponent, and the method further comprises placing the structurallycolored component within an internal cavity of the bladder prior toinflating the bladder Clause 113. The method of any of the precedingclauses, wherein the component is selected from a spacer formed of asolid polymeric material, a spacer formed of a foamed polymericmaterial, a spacer formed of a textile, or a combination thereof.Clause 114. The method of any preceding method clause, wherein thearticle is an article of any preceding article clause.Clause 115. An article, comprising a bladder formed using the methods of82-99.Clause 116. An inflated bladder for use in an article of footwear, theinflated bladder comprising:

a bladder wall having an interior-facing side and an exterior-facingside, wherein the interior-facing side defines at least a portion of aninterior region of the inflated bladder, and wherein the bladder wallfurther includes an average wall thickness between the interior-facingside and exterior-facing side that is less than 5 millimeters; and amulti-layer optical film having a first side and a second opposing side,wherein the first side of the multi-layer optical film is operablydisposed on the exterior-facing side of the bladder wall, and whereinthe multi-layer optical film imparts a structural color to the bladderwall.

Clause 117. The inflated bladder of any of the preceding clause, whereinthe bladder wall exhibits a gas transmission rate of 15 cm³/m²·atm·dayor less.

Clause 118. The inflated bladder of any of the preceding clause, whereinthe bladder wall further comprises alternating first and secondpolymeric layers, wherein the first polymeric layers each comprise oneor more thermoplastic polyurethanes, and wherein the second polymericlayers each comprise one or more thermoplastic ethylene-vinyl alcoholpolymers.Clause 119. The inflated bladder of any of the preceding clause, whereinthe bladder wall comprises one or more thermoplastic polyurethanes.Clause 120. The inflated bladder of any of the preceding clause, whereinthe multi-layer optical film comprises:

a first layer compositionally comprising a non-oxide metal; and

a second layer compositionally comprising a first metal oxide.

Clause 121. The inflated bladder of any of the preceding clause, andfurther comprising a third layer compositionally comprising a secondmetal oxide that is different from the first metal oxide.

Clause 122. The inflated bladder of any of the preceding clause, whereinthe multi-layer optical film comprises:

a first layer compositionally comprising a first metal oxide; and

a second layer compositionally comprising a second metal oxide differentfrom the first metal oxide.

Clause 123. The inflated bladder of any of the preceding clause, furthercomprising a primer layer disposed on the exterior-facing side of thebladder wall, and wherein the first side of the multi-layer optical filmis disposed on the primer layer.

Clause 124. The inflated bladder of any of the preceding clause, whereinthe primer layer has a thickness ranging from about 10 to about 100micrometers.

Clause 125. A bladder for use in an article of footwear, the bladdercomprising:

a bladder wall having an interior-facing side and an exterior-facingside, wherein the interior-facing side defines at least a portion of aninterior region of the bladder;

a plurality of topographical structures extending from theexterior-facing side of the bladder wall; and

a multi-layer optical film having a first side and a second opposingside, wherein the first side of the multi-layer optical film is disposedon the exterior-facing side of the bladder wall and covering theplurality of topographical structures, and wherein the multi-layeroptical film imparts a structural color to the bladder wall.

Clause 126. The inflated bladder of any of the preceding clause, whereinthe multi-layer optical film comprises:

a first layer compositionally comprising a first metal oxide, whereinthe first layer at least partially conforms to the plurality oftopographical structures; and

a second layer disposed on the first layer and compositionallycomprising a second metal oxide different from the first metal oxide.

Clause 127. The inflated bladder of any of the preceding clause, andfurther comprising a gas retained within the interior region of thebladder.

Clause 128. The inflated bladder of any of the preceding clause, whereinthe gas consists essentially of nitrogen.

Clause 129. The inflated bladder of any of the preceding clause, whereinthe bladder wall exhibits a gas transmission rate of 15 cm³/m²·atm·dayor less.

Clause 130. An article of footwear comprising:

a footwear upper; and

an inflated bladder comprising:

a top wall operably secured to the footwear upper;

a bottom wall opposite the top wall; and

one or more sidewalls extending between the top wall and the bottom wallof the inflated bladder, wherein the top wall, the bottom wall, and theone or more sidewalls collectively define an interior region of theinflated bladder, and wherein the one or more sidewalls each comprise anexterior-facing side; and a multi-layer optical film operably disposedon the exterior-facing side at least one of the one or more sidewalls toimpart a structural color to the one or more sidewalls.

Clause 131. The article of footwear of any of the preceding clauses,wherein the inflated bladder further comprises a plurality oftopographical structures extending from the exterior-facing side of atleast one of the one or more sidewalls such that the multi-layer opticalfilm covers the plurality of topographical structures.Clause 132. The article of footwear of any of the preceding clauses,wherein the multi-layer optical film comprises:

a first layer compositionally comprising a first metal oxide, whereinthe first layer at least partially conforms to the plurality oftopographical structures; and

a second layer disposed on the first layer and compositionallycomprising a second metal oxide different from the first metal oxide.

Clause 133. The article of footwear of any of the preceding clauses,wherein the structural color imparted to the one or more sidewalls has asingle hue regardless of viewing angle. Clause 134. The article offootwear of any of the preceding clauses, wherein the structural colorimparted to the one or more sidewalls has a metallic appearancecomprises a metallic color.Clause 135. The article of footwear of any of the preceding clauses,wherein the structural color imparted to the one or more sidewalls hastwo or more hues.Clause 136. A method of making a bladder, comprising:

disposing an multi-layer optical film onto an exterior-facing side or aninterior-facing side of a first bladder wall of a bladder, wherein theinterior-facing side defines at least a portion of an interior region ofthe inflated bladder, and wherein the bladder wall further includes anaverage wall thickness between the interior-facing side andexterior-facing side that is less than 5 millimeters, wherein themulti-layer optical film having a first side and a second opposing side,wherein the first side of the multi-layer optical film is operablydisposed on the exterior-facing side of the bladder wall, and whereinthe multi-layer optical film imparts a structural color to the bladderwall.

Clause 137. The method of footwear of any of the preceding clauses,wherein the method further comprises forming the bladder by applyingheat, pressure, vacuum, or a combination thereof to a film, forming thebladder;

wherein the step of forming the bladder is conducted prior to orfollowing the operably disposing the multi-layer optical film onto theexterior-facing side or the internal-facing side of the bladder wall.

Clause 138. The method of footwear of any of the preceding clauses,wherein the methods include the articles of the preceding clauses.

Clause 139. A bladder for use in an article of footwear, the bladdercomprising:

a bladder wall having an interior-facing side and an exterior-facingside, wherein the interior-facing side defines at least a portion of aninterior region of the bladder;

-   -   a plurality of topographical structures extending from the        exterior-facing side of the bladder wall; and    -   a multi-layer optical film having a first side and a second        opposing side, wherein the first side of the multi-layer optical        film is disposed on the exterior-facing side of the bladder wall        and covering the plurality of topographical structures, and        wherein the multi-layer optical film imparts a structural color        to the bladder wall.        Clause 140. A method of making a bladder, comprising:

disposing an multi-layer optical film onto an exterior-facing side or aninterior-facing side of a first bladder wall of a bladder, wherein theinterior-facing side defines at least a portion of an interior region ofthe inflated bladder, wherein a plurality of topographical structuresextending from the exterior-facing side of the bladder wall, wherein themulti-layer optical film having a first side and a second opposing side,wherein the first side of the multi-layer optical film is disposed onthe exterior-facing side of the bladder wall and covering the pluralityof topographical structures, and wherein the multi-layer optical filmimparts a structural color to the bladder wall.

Clause 141. A method of making an article of footwear comprising:

operably securing an inflated bladder to a top wall of a footwear upper,wherein the bladder comprises the top wall, a bottom wall opposite thetop wall; and one or more sidewalls extending between the top wall andthe bottom wall of the inflated bladder, wherein the top wall, thebottom wall, and the one or more sidewalls collectively define aninterior region of the inflated bladder, and wherein the one or moresidewalls each comprise an exterior-facing side; and a multi-layeroptical film operably disposed on the exterior-facing side at least oneof the one or more sidewalls to impart a structural color to the one ormore sidewalls.

It should be noted that ratios, concentrations, amounts, and othernumerical data may be expressed herein in a range format. It is to beunderstood that such a range format is used for convenience and brevity,and thus, should be interpreted in a flexible manner to include not onlythe numerical values explicitly recited as the limits of the range, butalso to include all the individual numerical values or sub-rangesencompassed within that range as if each numerical value and sub-rangeis explicitly recited. To illustrate, a concentration range of “about0.1 percent to about 5 percent” should be interpreted to include notonly the explicitly recited concentration of about 0.1 weight percent toabout 5 weight percent but also include individual concentrations (e.g.,1 percent, 2 percent, 3 percent, and 4 percent) and the sub-ranges(e.g., 0.5 percent, 1.1 percent, 2.2 percent, 3.3 percent, and 4.4percent) within the indicated range. The term “about” can includetraditional rounding according to significant figures of the numericalvalue. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ toabout ‘y’”.

Many variations and modifications may be made to the above-describedaspects. All such modifications and variations are intended to beincluded herein within the scope of this disclosure and protected by thefollowing claims.

What is claimed is:
 1. A bladder comprising: a bladder wall having aninterior-facing side and an exterior-facing side, wherein theinterior-facing side defines at least a portion of an interior region ofthe bladder, and wherein the bladder wall further includes an averagewall thickness between the interior-facing side and exterior-facing sidethat is less than 5 millimeters; and a multi-layer optical film having afirst side and a second opposing side, wherein the first side of themulti-layer optical film is operably disposed on the exterior-facingside of the bladder wall, and wherein the multi-layer optical filmimparts a structural color to the bladder wall, the multi-layer opticalfilm comprising a multilayer filter or multilayer reflector such thatthe structural color has a single hue regardless of viewing angle ormultihued having two or more hues where the hue changes abruptly betweenhues as the angle of observation or illumination changes.
 2. The bladderof claim 1, wherein the bladder wall exhibits a nitrogen gastransmission rate of 15 cm³/m²·atm·day or less.
 3. The bladder of claim1, wherein the bladder wall further comprises alternating first andsecond polymeric layers, wherein the first polymeric layers eachcomprise one or more thermoplastic polyurethanes, and wherein the secondpolymeric layers each comprise one or more thermoplastic ethylene-vinylalcohol polymers.
 4. The bladder of claim 1, wherein the bladder wallcomprises one or more thermoplastic polyurethanes.
 5. The bladder ofclaim 1, wherein the multi-layer optical film comprises: a first layercompositionally comprising a non-oxide metal; and a second layercompositionally comprising a first metal oxide.
 6. The bladder of claim5, and further comprising a third layer compositionally comprising asecond metal oxide that is different from the first metal oxide.
 7. Thebladder of claim 1, wherein the multi-layer optical film comprises: afirst layer compositionally comprising a first metal oxide; and a secondlayer compositionally comprising a second metal oxide different from thefirst metal oxide.
 8. The bladder of claim 1, further comprising aprimer layer disposed on the exterior-facing side of the bladder wall,and wherein the first side of the multi-layer optical film is disposedon the primer layer.
 9. The bladder of claim 1, wherein the bladder isan inflated bladder and further comprises a gas retained within theinterior region of the bladder.
 10. The bladder of claim 1, wherein thebladder further comprises a plurality of topographical structuresextending from the exterior-facing side of at least one of the one ormore sidewalls such that the multi-layer optical film covers theplurality of topographical structures.
 11. The bladder of claim 1,wherein each color visible at each possible angle of observation isassigned to a single hue selected from the group consisting of theprimary, secondary and tertiary colors on the red yellow blue (RYB)color wheel, all of the assigned hues fall into a single hue group,wherein the single hue group is one of a) green-yellow, yellow, andyellow-orange; b) yellow, yellow-orange and orange; c) yellow-orange,orange, and orange-red; d) orange-red, and red-purple; e) red,red-purple, and purple; f) red-purple, purple, and purple-blue; g)purple, purple-blue, and blue; h) purple-blue, blue, and blue-green; i)blue, blue-green and green; and j) blue-green, green, and green-yellow.12. The bladder of claim 1, wherein a hue of the imparted structuralcolor includes blue, blue-green, purple-blue, cyan, or indigo.
 13. Thebladder of claim 1, wherein the multi-layer optical film comprises amultilayer reflector having at least two adjacent layers havingdifferent refractive indices, wherein at least one of the layers of themultilayer reflector has a thickness that is about one fourth of thewavelength of visible light to be reflected by the multi-layer opticalfilm to impart the structural color.
 14. The bladder of claim 1, whereinthe bladder is a cushioning element for an article of footwear.
 15. Amethod of making a bladder, the method comprising: operably disposing amulti-layer optical film onto an exterior-facing side of a first bladderwall of a bladder, wherein the multi-layer optical film has a first sideand a second opposing side, wherein the first side of the multi-layeroptical film or the second side of the multi-layer optical film isdisposed on the exterior-facing side of the bladder wall, and whereinthe multi-layer optical film imparts a structural color to the bladderwall, and wherein the multi-layer optical film comprising a multilayerfilter or multilayer reflector such that the structural color has asingle hue regardless of viewing angle or multihued having two or morehues where the hue changes abruptly between hues as the angle ofobservation or illumination changes.
 16. The method of claim 15, furthercomprising disposing a primer layer onto the exterior-facing side priorto the step of operably disposing the multi-layer optical film, andwherein the step of disposing the primer layer comprises depositing ametal oxide using a deposition process.
 17. The method of claim 15,wherein the multi-layer optical film comprises: a first layercompositionally comprising a first metal oxide; and a second layercompositionally comprising a second metal oxide different from the firstmetal oxide.
 18. The method of claim 15, wherein the bladder furthercomprises a plurality of topographical structures extending from theexterior-facing side of at least one of the one or more sidewalls suchthat the multi-layer optical film covers the plurality of topographicalstructures.
 19. The method of claim 15, wherein each color visible ateach possible angle of observation is assigned to a single hue selectedfrom the group consisting of the primary, secondary and tertiary colorson the red yellow blue (RYB) color wheel, all of the assigned hues fallinto a single hue group, wherein the single hue group is one of a)green-yellow, yellow, and yellow-orange; b) yellow, yellow-orange andorange; c) yellow-orange, orange, and orange-red; d) orange-red, andred-purple; e) red, red-purple, and purple; f) red-purple, purple, andpurple-blue; g) purple, purple-blue, and blue; h) purple-blue, blue, andblue-green; i) blue, blue-green and green; and j) blue-green, green, andgreen-yellow.
 20. The method of claim 15, wherein the structural colorimparted to the bladder wall has a metallic appearance.